Polymerization process

ABSTRACT

The invention provides for polymerization catalyst compositions, and for methods for introducing the catalyst compositions into a polymerization reactor. More particularly, the method combines a catalyst component containing slurry and a catalyst component containing solution to form the completed catalyst composition for introduction into the polymerization reactor. The invention is also directed to methods of preparing the catalyst component slurry, the catalyst component solution and the catalyst compositions, to methods of controlling the properties of polymer products utilizing the catalyst compositions, and to polymers produced therefrom.

STATEMENT OF RELATED APPLICATIONS

This application is a Continuation Application claiming priority to U.S.application Ser. No. 10/459,160 filed on Jun. 11, 2003, now abandoned,which is a Divisional and claims priority of U.S. application Ser. No.09/729,453, filed Dec. 4, 2000, now issued as U.S. Pat. No. 6,608,149B2.

FIELD OF THE INVENTION

The invention relates to a process for polymerizing olefin(s).Generally, the invention relates to polymerization catalystcompositions, and to methods for introducing the catalyst compositionsinto a polymerization reactor. More particularly, the method combines acatalyst component slurry with a catalyst component solution to form thecompleted catalyst composition for introduction into the polymerizationreactor. The invention also relates to methods of preparing the catalystcomponent slurries, the catalyst component solutions, and the catalystcompositions, to methods of controlling the properties of polymerproducts utilizing the catalyst compositions, and to polymers producedtherefrom.

BACKGROUND OF THE INVENTION

Advances in polymerization and catalysis have resulted in the capabilityto produce many new polymers having improved physical and chemicalproperties useful in a wide variety of superior products andapplications. With the development of new catalysts the choice ofpolymerization (solution, slurry, high pressure or gas phase) forproducing a particular polymer has been greatly expanded. Also, advancesin polymerization technology have provided more efficient, highlyproductive and economically enhanced processes. Especially illustrativeof these advances is the development of technology utilizing bulkyligand metallocene catalyst systems and other advanced metallocene-typecatalyst systems.

To utilize these systems in industrial slurry or gas phases processes,it is useful that the catalyst compound be immobilized on a carrier orsupport such as, for example silica or alumina. The use of supported orheterogeneous catalysts increases process efficiencies by assuring thatthe forming polymeric particles achieve a shape and density thatimproves reactor operability and ease of handling. However, bulky ligandmetallocene and metallocene-type catalysts typically exhibit loweractivity when supported than when utilized in unsupported or homogeneousform. This “support effect” makes commercialization of these promisingcatalyst systems more difficult.

U.S. Pat. Nos. 5,317,036 and 5,693,727 and European publication EP-A-0593 083 and PCT publication WO 97/46599 all describe various processesand techniques for introducing liquid unsupported catalysts to apolymerization reactor.

U.S. Pat. No. 6,069,213 discloses combining a supported and anunsupported metallocene catalysts in the polymerization of olefins,European publication EP 0 965 601A disclose a combination of a solidZiegler-Natta catalyst with a liquid catalyst in toluene or Kaydolactivated with methyl alumoxane or modified methyl alumoxane, andChinese Published Patent Application No. 97116451.7 discloses combiningan unsupported metallocene with a supported methylalumoxane. None ofthese references, however, discloses a catalyst composition prepared bycontinuously combining a catalyst component slurry with a catalystcomponent solution, then introducing the combination into an operatingpolymerization reactor.

While all these methods have been described in the art, there exists aneed to reduce the support effect for bulky ligand metallocene andmetallocene-type polymerization catalyst compositions, for an improvedmethod for introducing catalyst compositions, and especially forintroducing mixed catalyst compositions, into a polymerization reactors,and for methods to control the properties of polymer products utilizingsuch catalyst compositions.

SUMMARY OF THE INVENTION

The invention generally provides polymerization catalyst compositionsand methods for introducing the catalyst compositions into apolymerization reactor. More particularly, the method combines acatalyst component containing slurry and a catalyst component containingsolution to form the completed catalyst composition for introductioninto the polymerization reactor. The invention is also directed tomethods of preparing the catalyst component slurry, the catalystcomponent solution, and the catalyst compositions, to methods ofcontrolling the properties of polymer products utilizing the catalystcompositions, and to polymers produced therefrom.

In one aspect, the invention provides a process to polymerize olefin(s)which includes the steps of continuously combining a catalyst componentslurry with a catalyst component solution to form a catalyst compositionand introducing the catalyst composition and one or more olefin(s) intoan operating polymerization reactor.

In another aspect, the invention provides a process to control polymerproperties which includes the steps of continuously combining a catalystcomponent slurry with a catalyst component solution to form a catalystcomposition, introducing the catalyst composition into a polymerizationreactor with one or more olefin(s) to form a polymer product, measuringa sample of the polymer product to obtain an initial product propertyand changing a process parameter to obtain a second product property.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates an embodiment of one equipment configuration toutilize the invention.

FIG. 2 illustrates the catalyst feed configuration used for Example 2.

FIG. 3 illustrates the catalyst feed configuration used for Example 3.

FIG. 4 illustrates the catalyst feed configuration used for Example 4.

FIG. 5 is a typical SEC curve of one embodiment of the polymer.

DETAILED DESCRIPTION OF THE INVENTION I. Introduction

The components of the catalyst composition of the invention includecatalyst compounds, activator compounds and support materials. Thecatalyst components are utilized in a slurry and/or in a solution wherethe slurry and solution are combined then introduced into apolymerization reactor.

II. Catalyst Compounds

The catalyst compounds which may be utilized in the catalystcompositions of the invention include invention include: Group 15containing metal compounds; bulky ligand metallocene compounds;phenoxide catalyst compounds; additionally discovered catalystcompounds; and conventional-type transition metal catalysts.

A. Group 15 Containing Metal Catalyst Compound

The catalyst composition of the invention may include one or more Group15 containing metal catalyst compounds. The Group 15 containing compoundgenerally includes a Group 3 to 14 metal atom, preferably a Group 3 to7, more preferably a Group 4 to 6, and even more preferably a Group 4metal atom, bound to at least one leaving group and also bound to atleast two Group 15 atoms, at least one of which is also bound to a Group15 or 16 atom through another group.

In one embodiment, at least one of the Group 15 atoms is also bound to aGroup 15 or 16 atom through another group which may be a C₁ to C₂₀hydrocarbon group, a heteroatom containing group, silicon, germanium,tin, lead, or phosphorus, wherein the Group 15 or 16 atom may also bebound to nothing or a hydrogen, a Group 14 atom containing group, ahalogen, or a heteroatom containing group, and wherein each of the twoGroup 15 atoms are also bound to a cyclic group and may optionally bebound to hydrogen, a halogen, a heteroatom or a hydrocarbyl group, or aheteroatom containing group.

In another embodiment, the Group 15 containing metal compound of thepresent invention may be represented by the formulae:

wherein

M is a Group 3 to 12 transition metal or a Group 13 or 14 main groupmetal, preferably a Group 4, 5, or 6 metal, and more preferably a Group4 metal, and most preferably zirconium, titanium or hafnium,

each X is independently a leaving group, preferably, an anionic leavinggroup, and more preferably hydrogen, a hydrocarbyl group, a heteroatomor a halogen, and most preferably an alkyl.

y is 0 or 1 (when y is 0 group L′ is absent),

n is the oxidation state of M, preferably +3, +4, or +5, and morepreferably +4,

m is the formal charge of the YZL or the YZL′ ligand, preferably 0, −1,−2 or −3, and more preferably −2,

L is a Group 15 or 16 element, preferably nitrogen,

L′ is a Group 15 or 16 element or Group 14 containing group, preferablycarbon, silicon or germanium,

Y is a Group 15 element, preferably nitrogen or phosphorus, and morepreferably nitrogen,

Z is a Group 15 element, preferably nitrogen or phosphorus, and morepreferably nitrogen,

R¹ and R² are independently a C₁ to C₂₀ hydrocarbon group, a heteroatomcontaining group having up to twenty carbon atoms, silicon, germanium,tin, lead, halogen or phosphorus, preferably a C₂ to C₂₀ alkyl, aryl oraralkyl group, more preferably a linear, branched or cyclic C₂ to C₂₀alkyl group, most preferably a C₂ to C₆ hydrocarbon group. R¹ and R² mayalso be interconnected to each other.

R³ is absent or a hydrocarbon group, hydrogen, a halogen, a heteroatomcontaining group, preferably a linear, cyclic or branched alkyl grouphaving 1 to 20 carbon atoms, more preferably R³ is absent, hydrogen oran alkyl group, and most preferably hydrogen

R⁴ and R⁵ are independently an alkyl group, an aryl group, substitutedaryl group, a cyclic alkyl group, a substituted cyclic alkyl group, acyclic aralkyl group, a substituted cyclic aralkyl group or multiplering system, preferably having up to 20 carbon atoms, more preferablybetween 3 and 10 carbon atoms, and even more preferably a C₁ to C₂₀hydrocarbon group, a C₁ to C₂₀ aryl group or a C₁ to C₂₀ aralkyl group,or a heteroatom containing group, for example PR₃, where R is an alkylgroup,

R¹ and R² may be interconnected to each other, and/or R⁴ and R⁵ may beinterconnected to each other,

R⁶ and R⁷ are independently absent, or hydrogen, an alkyl group,halogen, heteroatom or a hydrocarbyl group, preferably a linear, cyclicor branched alkyl group having 1 to 20 carbon atoms, more preferablyabsent, and

R* is absent, or is hydrogen, a Group 14 atom containing group, ahalogen, or a heteroatom containing group.

By “formal charge of the YZL or YZL′ ligand”, it is meant the charge ofthe entire ligand absent the metal and the leaving groups X.

By “R¹ and R² may also be interconnected” it is meant that R¹ and R² maybe directly bound to each other or may be bound to each other throughother groups. By “R⁴ and R⁵ may also be interconnected” it is meant thatR⁴ and R⁵ may be directly bound to each other or may be bound to eachother through other groups.

An alkyl group may be a linear, branched alkyl radicals, or alkenylradicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acylradicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An aralkyl group is defined to be a substitutedaryl group.

In a preferred embodiment R⁴ and R⁵ are independently a grouprepresented by the following formula:

wherein

R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkyl group, ahalide, a heteroatom, a heteroatom containing group containing up to 40carbon atoms, preferably a C₁ to C₂₀ linear or branched alkyl group,preferably a methyl, ethyl, propyl or butyl group, any two R groups mayform a cyclic group and/or a heterocyclic group. The cyclic groups maybe aromatic. In a preferred embodiment R⁹, R¹⁰ and R¹² are independentlya methyl, ethyl, propyl or butyl group (including all isomers), in apreferred embodiment R⁹, R¹⁰ and R¹² are methyl groups, and R⁸ and R¹¹are hydrogen.

In a particularly preferred embodiment R⁴ and R⁵ are both a grouprepresented by the following formula:

In this embodiment, M is a Group 4 metal, preferably zirconium, titaniumor hafnium, and even more preferably zirconium; each of L, Y, and Z isnitrogen; each of R¹ and R² is —CH₂—CH₂—; R³ is hydrogen; and R⁶ and R⁷are absent.

In a particularly preferred embodiment the Group 15 containing metalcompound is represented by Compound 1 below:

In compound 1, Ph equals phenyl.

The Group 15 containing metal compounds utilized in the catalystcomposition of the invention are prepared by methods known in the art,such as those disclosed in EP 0 893 454 A1, U.S. Pat. No. 5,889,128 andthe references cited in U.S. Pat. No. 5,889,128 which are all hereinincorporated by reference. U.S. application Ser. No. 09/312,878, filedMay 17, 1999, discloses a gas or slurry phase polymerization processusing a supported bisamide catalyst, which is also incorporated hereinby reference.

A preferred direct synthesis of these compounds comprises reacting theneutral ligand, (see for example YZL or YZL′ of formula I or II) withM^(n)X_(n) (M is a Group 3 to 14 metal, n is the oxidation state of M,each X is an anionic group, such as halide, in a non-coordinating orweakly coordinating solvent, such as ether, toluene, xylene, benzene,methylene chloride, and/or hexane or other solvent having a boilingpoint above 60° C., at about 20 to about 150° C. (preferably 20 to 100°C.), preferably for 24 hours or more, then treating the mixture with anexcess (such as four or more equivalents) of an alkylating agent, suchas methyl magnesium bromide in ether. The magnesium salts are removed byfiltration, and the metal complex isolated by standard techniques.

In one embodiment the Group 15 containing metal compound is prepared bya method comprising reacting a neutral ligand, (see for example YZL orYZL′ of formula I or II) with a compound represented by the formulaM^(n)X_(n) (where M is a Group 3 to 14 metal, n is the oxidation stateof M, each X is an anionic leaving group) in a non-coordinating orweakly coordinating solvent, at about 20° C. or above, preferably atabout 20 to about 100° C., then treating the mixture with an excess ofan alkylating agent, then recovering the metal complex. In a preferredembodiment the solvent has a boiling point above 60° C., such astoluene, xylene, benzene, and/or hexane. In another embodiment thesolvent comprises ether and/or methylene chloride, either beingpreferable.

For additional information of Group 15 containing metal compounds,please see Mitsui Chemicals, Inc. in EP 0 893 454 A1 which disclosestransition metal amides combined with activators to polymerize olefins.

In one embodiment the Group 15 containing metal compound is allowed toage prior to use as a polymerization. It has been noted on at least oneoccasion that one such catalyst compound (aged at least 48 hours)performed better than a newly prepared catalyst compound.

B. Bulky Ligand Metallocene Compounds

The catalyst composition of the invention may include one or more bulkyligand metallocene compounds (also referred to herein as metallocenes).

Generally, bulky ligand metallocene compounds include half and fullsandwich compounds having one or more bulky ligands bonded to at leastone metal atom. Typical bulky ligand metallocene compounds are generallydescribed as containing one or more bulky ligand(s) and one or moreleaving group(s) bonded to at least one metal atom.

The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.These bulky ligands, preferably the ring(s) or ring system(s) aretypically composed of atoms selected from Groups 13 to 16 atoms of thePeriodic Table of Elements, preferably the atoms are selected from thegroup consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum or a combination thereof.Most preferably, the ring(s) or ring system(s) are composed of carbonatoms such as but not limited to those cyclopentadienyl ligands orcyclopentadienyl-type ligand structures or other similar functioningligand structure such as a pentadiene, a cyclooctatetraendiyl or animide ligand. The metal atom is preferably selected from Groups 3through 15 and the lanthanide or actinide series of the Periodic Tableof Elements. Preferably the metal is a transition metal from Groups 4through 12, more preferably Groups 4, 5 and 6, and most preferably thetransition metal is from Group 4.

In one embodiment, the catalyst composition of the invention includesone or more bulky ligand metallocene catalyst compounds represented bythe formula:

L^(A)L^(B)MQ_(n)  (III)

where M is a metal atom from the Periodic Table of the Elements and maybe a Group 3 to 12 metal or from the lanthanide or actinide series ofthe Periodic Table of Elements, preferably M is a Group 4, 5 or 6transition metal, more preferably M is a Group 4 transition metal, evenmore preferably M is zirconium, hafnium or titanium. The bulky ligands,L^(A) and L^(B), are open, acyclic or fused ring(s) or ring system(s)and are any ancillary ligand system, including unsubstituted orsubstituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands,heteroatom substituted and/or heteroatom containingcyclopentadienyl-type ligands. Non-limiting examples of bulky ligandsinclude cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands,indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of π-bonding to M. In yetanother embodiment, the atomic molecular weight (MW) of L^(A) or L^(B)exceeds 60 a.m.u., preferably greater than 65 a.m.u. In anotherembodiment, L^(A) and L^(B) may comprise one or more heteroatoms, forexample, nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof Formula III only one of either L^(A) or L^(B) is present.

Independently, each L^(A) and L^(B) may be unsubstituted or substitutedwith a combination of substituent groups R. Non-limiting examples ofsubstituent groups R include one or more from the group selected fromhydrogen, or linear, branched alkyl radicals, or alkenyl radicals,alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals,aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonylradicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals,acyloxy radicals, acylamino radicals, aroylamino radicals, straight,branched or cyclic, alkylene radicals, or combination thereof. In apreferred embodiment, substituent groups R have up to 50 non-hydrogenatoms, preferably from 1 to 30 carbon, that can also be substituted withhalogens or heteroatoms or the like. Non-limiting examples of alkylsubstituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, includingall their isomers, for example tertiary butyl, isopropyl, and the like.Other hydrocarbyl radicals include fluoromethyl, fluoroethyl,difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbylsubstituted organometalloid radicals including trimethylsilyl,trimethylgermyl, methyldiethylsilyl and the like; andhalocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methy-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

Other ligands may be bonded to the metal M, such as at least one leavinggroup Q. In one embodiment, Q is a monoanionic labile ligand having asigma-bond to M. Depending on the oxidation state of the metal, thevalue for n is 0, 1 or 2 such that Formula III above represents aneutral bulky ligand metallocene catalyst compound.

Non-limiting examples of Q ligands include weak bases such as amines,phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals havingfrom 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike.

In another embodiment, the catalyst composition of the invention mayinclude one or more bulky ligand metallocene catalyst compounds whereL^(A) and L^(B) of Formula III are bridged to each other by at least onebridging group, A, as represented by Formula IV.

L^(A)AL^(B)MQ_(n)  (IV)

The compounds of Formula IV are known as bridged, bulky ligandmetallocene catalyst compounds. L^(A), L^(B), M, Q and n are as definedabove. Non-limiting examples of bridging group A include bridging groupscontaining at least one Group 13 to 16 atom, often referred to as adivalent moiety such as but not limited to at least one of a carbon,oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom or acombination thereof. Preferably bridging group A contains a carbon,silicon or germanium atom, most preferably A contains at least onesilicon atom or at least one carbon atom. The bridging group A may alsocontain substituent groups R as defined above including halogens andiron. Non-limiting examples of bridging group A may be represented byR′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ is independently, aradical group which is hydride, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, hydrocarbyl-substitutedorganometalloid, halocarbyl-substituted organometalloid, disubstitutedboron, disubstituted pnictogen, substituted chalcogen, or halogen or twoor more R′ may be joined to form a ring or ring system. In oneembodiment, the bridged, bulky ligand metallocene catalyst compounds ofFormula IV have two or more bridging groups A (EP 664 301 B1).

In another embodiment, the bulky ligand metallocene catalyst compoundsare those where the R substituents on the bulky ligands L^(A) and L^(b)of Formulas III and IV are substituted with the same or different numberof substituents on each of the bulky ligands. In another embodiment, thebulky ligands L^(A) and L^(B) of Formulas III and IV are different fromeach other.

Other bulky ligand metallocene catalyst compounds and catalyst systemsuseful in the invention may include those described in U.S. Pat. Nos.5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208,5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398,5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158, 5,900,517 and5,939,503 and PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO99/14221 and European publications EP-A-0 578 838, EP-A-0 638 595,EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819,EP-B1-0 748 821 and EP-B1-0 757 996, all of which are herein fullyincorporated by reference.

In another embodiment, the catalyst compositions of the invention mayinclude bridged heteroatom, mono-bulky ligand metallocene compounds.These types of catalysts and catalyst systems are described in, forexample, PCT publication WO 92/00333, WO 94/07928, WO 91/04257, WO94/03506, WO96/00244, WO 97/15602 and WO 99/20637 and U.S. Pat. Nos.5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 andEuropean publication EP-A-0 420 436, all of which are herein fullyincorporated by reference.

In another embodiment, the catalyst composition of the inventionincludes one or more bulky ligand metallocene catalyst compoundsrepresented by Formula V:

L^(C)AJMQ_(n)  (V)

where M is a Group 3 to 16 metal atom or a metal selected from the Groupof actinides and lanthanides of the Periodic Table of Elements,preferably M is a Group 4 to 12 transition metal, and more preferably Mis a Group 4, 5 or 6 transition metal, and most preferably M is a Group4 transition metal in any oxidation state, especially titanium; L^(C) isa substituted or unsubstituted bulky ligand bonded to M; J is bonded toM; A is bonded to J and L^(C); J is a heteroatom ancillary ligand; and Ais a bridging group; Q is a univalent anionic ligand; and n is theinteger 0, 1 or 2. In Formula V above, L^(C), A and J form a fused ringsystem. In an embodiment, L^(C) of Formula V is as defined above forL^(A). A, M and Q of Formula V are as defined above in Formula III.

In Formula V J is a heteroatom containing ligand in which J is anelement with a coordination number of three from Group 15 or an elementwith a coordination number of two from Group 16 of the Periodic Table ofElements. Preferably J contains a nitrogen, phosphorus, oxygen or sulfuratom with nitrogen being most preferred.

In an embodiment of the invention, the bulky ligand metallocene catalystcompounds are heterocyclic ligand complexes where the bulky ligands, thering(s) or ring system(s), include one or more heteroatoms or acombination thereof. Non-limiting examples of heteroatoms include aGroup 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen,aluminum, silicon, phosphorous and tin. Examples of these bulky ligandmetallocene catalyst compounds are described in WO 96/33202, WO96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874 005 and U.S. Pat.No. 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417,and 5,856,258 all of which are herein incorporated by reference.

In one embodiment, the bulky ligand metallocene catalyst compounds arethose complexes known as transition metal catalysts based on bidentateligands containing pyridine or quinoline moieties, such as thosedescribed in U.S. application Ser. No. 09/103,620 filed Jun. 23, 1998,which is herein incorporated by reference. In another embodiment, thebulky ligand metallocene catalyst compounds are those described in PCTpublications WO 99/01481 and WO 98/42664, which are fully incorporatedherein by reference.

In another embodiment, the bulky ligand metallocene catalyst compound isa complex of a metal, preferably a transition metal, a bulky ligand,preferably a substituted or unsubstituted pi-bonded ligand, and one ormore heteroallyl moieties, such as those described in U.S. Pat. Nos.5,527,752 and 5,747,406 and EP-B1-0 735 057, all of which are hereinfully incorporated by reference.

In another embodiment, the catalyst composition of the inventionincludes one or more bulky ligand metallocene catalyst compounds isrepresented by Formula VI:

L^(D)MQ₂(YZ)X_(n)  (VI)

where M is a Group 3 to 16 metal, preferably a Group 4 to 12 transitionmetal, and most preferably a Group 4, 5 or 6 transition metal; L^(D) isa bulky ligand that is bonded to M; each Q is independently bonded to Mand Q₂(YZ) forms a ligand, preferably a unicharged polydentate ligand;or Q is a univalent anionic ligand also bonded to M; X is a univalentanionic group when n is 2 or X is a divalent anionic group when n is 1;n is 1 or 2.

In Formula VI, L and M are as defined above for Formula III. Q is asdefined above for Formula III, preferably Q is selected from the groupconsisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

In another embodiment, the bulky ligand metallocene catalyst compoundsare those described in PCT publications WO 99/01481 and WO 98/42664,which are fully incorporated herein by reference.

Useful Group 6 bulky ligand metallocene catalyst systems are describedin U.S. Pat. No. 5,942,462, which is incorporated herein by reference.

Still other useful catalysts include those multinuclear metallocenecatalysts as described in WO 99/20665 and U.S. Pat. No. 6,010,794, andtransition metal metaaracyle structures described in EP 0 969 101 A2,which are herein incorporated herein by reference. Other metallocenecatalysts include those described in EP 0 950 667 A1, doublecross-linked metallocene catalysts (EP 0 970 074 A1), tetheredmetallocenes (EP 970 963 A2) and those sulfonyl catalysts described inU.S. Pat. No. 6,008,394, which are incorporated herein by reference.

It is also contemplated that in one embodiment the bulky ligandmetallocene catalysts, described above, include their structural oroptical or enantiomeric isomers (meso and racemic isomers, for examplesee U.S. Pat. No. 5,852,143, incorporated herein by reference) andmixtures thereof.

It is further contemplated that any one of the bulky ligand metallocenecatalyst compounds, described above, have at least one fluoride orfluorine containing leaving group as described in U.S. application Ser.No. 09/191,916 filed Nov. 13, 1998.

Illustrative but non-limiting examples of bulky ligand metallocenecatalyst compounds include: bis(cyclopentadienyl)titanium dimethyl,bis(cyclopentadienyl)titanium diphenyl, bis(cyclopentadienyl)zirconiumdimethyl, bis(cyclopentadienyl)zirconium diphenyl,bis(cyclopentadienyl)haffium dimethyl or diphenyl,bis(cyclopentadienyl)titanium di-neopentyl,bis(cyclopentadienyl)zirconium di-neopentyl,bis(cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)zirconiumdibenzyl, bis(cyclopentadienyl)vanadium dimethyl,bis(cyclopentadienyl)titanium methyl chloride,bis(cyclopentadienyl)titanium ethyl chloride,bis(cyclopentadienyl)titanium phenyl chloride,bis(cyclopentadienyl)zirconium methyl chloride,bis(cyclopentadienyl)zirconium ethyl chloride,bis(cyclopentadienyl)zirconium phenyl chloride,bis(cyclopentadienyl)titanium methyl bromide, cyclopentadienyl titaniumtrimethyl, cyclopentadienyl zirconium triphenyl, cyclopentadienylzirconium trineopentyl, cyclopentadienyl zirconium trimethyl,cyclopentadienyl hafnium triphenyl, cyclopentadienyl hafniumtrineopentyl, cyclopentadienyl hafnium trimethyl,pentamethylcyclopentadienyl titanium trichloride,pentaethylcyclopentadienyl titanium trichloride, bis(indenyl)titaniumdiphenyl or dichloride, bis(methylcyclopentadienyl)titanium diphenyl ordihalide, bis(1,2-dimethylcyclopentadienyl)titanium diphenyl ordichloride, bis(1,2-diethylcyclopentadienyl)titanium diphenyl ordichloride, bis(pentamethyl cyclopentadienyl)titanium diphenyl ordichloride; dimethyl silyldicyclopentadienyl titanium diphenyl ordichloride, methyl phosphine dicyclopentadienyl titanium diphenyl ordichloride, methylenedicyclopentadienyl titanium diphenyl or dichloride,isopropyl(cyclopentadienyl)(fluorenyl)zirconium dichloride,isopropyl(cyclopentadienyl)(octahydrofluorenyl)zirconium dichloride,diisopropylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,diisobutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,ditertbutylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,diisopropylmethylene(2,5-dimethylcyclopentadienyl)(fluorenyl)zirconiumdichloride, isopropyl(cyclopentadienyl)(fluorenyl)hafniium dichloride,diphenylmethylene(cyclopentadienyl)(fluorenyl)hafniium dichloride,diisopropylmethylene(cyclopentadienyl)(fluorenyl)hafium dichloride,diisobutylmethylene(cyclopentadienyl)(fluorenyl)hafnium dichloride,ditertbutylmethylene(cyclopentadienyl)(fluorenyl) hafnium dichloride,cyclohexylidene(cyclopentadienyl)(fluorenyl)hafnium dichbride,diisopropylmethylene(2,5-dimethylcyclopentadienyl) (fluorenyl)-hafniumdichloride, isopropyl(cyclopentadienyl)(fluorenyl)titanium dichloride,diphenylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,diisopropylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,diisobutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,ditertbutylmethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,cyclohexylidene(cyclopentadienyl)(fluorenyl)titanium dichloride,diisopropylmethylene(2,5 -dimethylcyclopentadienyl fluorenyl)titaniumdichloride, racemic-ethylene bis(1-indenyl)zirconium (W) dichloride,racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV)dichloride, racemic-dimethylsilyl bis(1-indenyl)zirconium(IV)dichloride, racemic-dimethylsilylbis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV) dichloride,racemic-1,1,2,2-tetramethylsilanylene bis(1-indenyl)zirconium(IV)dichloride, racemic-1,1,2,2-tetramethylsilanylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium(IV) dichloride,ethylidene(1-indenyl tetramethylcyclopentadienyl)zirconium(IV)dichloride, racemic-dimethylsilylbis(2-methyl-4-t-butyl-1-cyclopentadienyl)zirconium(IV) dichloride,racemic-ethylene bis(1-indenyl)hafnium(IV) dichloride, racemic-ethylenebis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV) dichloride,racemic-dimethylsilyl bis(1-indenyl)hafnium(IV) dichloride,racemic-dimethylsilyl bis (4,5,6,7-tetrahydro-1-indenyl) hafnium(IV)dichloride, racemic-1,1,2,2-tetramethylsilanylenebis(1-indenyl)hafnium(IV) dichloride,racemic-1,1,2,2-tetramethylsilanylenebis(4,5,6,7-tetrahydro-1-indenyl)hafnium(IV), dichloride,ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)hafnium(IV)dichloride, racemic-ethylene bis(1-indenyl)titanium(IV) dichloride,racemic-ethylene bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride, racemic-dimethylsilyl bis(1-indenyl)titanium(IV) dichloride,racemic-dimethylsilyl bis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV)dichloride, racemic-1,1,2,2-tetramethylsilanylenebis(1-indenyl)titanium(IV) dichlorideracemic-1,1,2,2-tetramethylsilanylenebis(4,5,6,7-tetrahydro-1-indenyl)titanium(IV) dichloride, and ethylidene(1-indenyl-2,3,4,5-tetramethyl-1-cyclopentadienyl)titanium(IV)dichloride.

Preferred bulky ligand metallocene catalyst compounds arediphenylmethylene (cyclopentadienyl)(fluorenyl)zirconium dichloride,racemic-dimethylsilyl bis(2-methyl-1-indenyl) zirconium(IV) dichloride,racemic-dimethylsilyl bis(2-methyl-4-(1-naphthyl-1-indenyl)zirconium(IV) dichloride, and racemic-dimethylsilylbis(2-methyl-4-phenyl-1-indenyl) zirconium(IV) dichloride. Otherpreferred bulky ligand metallocene catalyst compounds include, indenylzirconium tris(diethylcarbamate), indenyl zirconium tris(pivalate),indenyl zirconium tris(p-toluate), indenyl zirconium tris(benzoate),(1-methylindenyl) zirconium tris(pivalate), (2-methylindenyl) zirconiumtris(diethylcarbamate), (methylcyclopentadienyl) zirconiumtris(pivalate), cyclopentadienyl tris(pivalate), and(pentamethylcyclopentadienyl) zirconium tris(benzoate).

C. Phenoxide Catalyst Compound

The catalyst composition of the invention may include one or morephenoxide catalyst compounds represented by the following formulae:

wherein R¹ is hydrogen or a C₄ to C₁₀₀ group, preferably a tertiaryalkyl group, preferably a C₄ to C₂₀ alkyl group, preferably a C₄ to C₂₀tertiary alkyl group, preferably a neutral C₄ to C₁₀₀ group and may ormay not also be bound to M, and at least one of R² to R⁵ is a groupcontaining a heteroatom, the rest of R² to R⁵ are independently hydrogenor a C₁ to C₁₀₀ group, preferably a C₄ to C₂₀ alkyl group (preferablybutyl, isobutyl, pentyl hexyl, heptyl, isohexyl, octyl, isooctyl, decyl,nonyl, dodecyl) and any of R² to R⁵ also may or may not be bound to M,

O is oxygen, M is a group 3 to group 10 transition metal or lanthanidemetal, preferably a group 4 metal, preferably Ti, Zr or Hf, n is thevalence state of the metal M, preferably 2, 3, 4, or 5, Q is an alkyl,halogen, benzyl, amide, carboxylate, carbamate, thiolate, hydride oralkoxide group, or a bond to an R group containing a heteroatom whichmay be any of R¹ to R⁵ A heteroatom containing group may be anyheteroatom or a heteroatom bound to carbon silica or another heteroatom.Preferred heteroatoms include boron, aluminum, silicon, nitrogen,phosphorus, arsenic, tin, lead, antimony, oxygen, selenium, tellurium.Particularly preferred heteroatoms include nitrogen, oxygen, phosphorus,and sulfur. Even more particularly preferred heteroatoms include oxygenand nitrogen. The heteroatom itself may be directly bound to thephenoxide ring or it may be bound to another atom or atoms that arebound to the phenoxide ring. The heteroatom containing group may containone or more of the same or different heteroatoms. Preferred heteroatomgroups include imines, amines, oxides, phosphines, ethers, ketenes,oxoazolines heterocyclics, oxazolines, thioethers, and the like.Particularly preferred heteroatom groups include imines. Any twoadjacent R groups may form a ring structure, preferably a 5 or 6membered ring. Likewise the R groups may form multi-ring structures. Inone embodiment any two or more R groups do not form a 5 membered ring.

In a preferred embodiment, Q is a bond to any of R² to R⁵ and the Rgroup that Q is bound to is a heteroatom containing group.

This invention may also be practiced with the catalysts disclosed in EP0 874 005 A1, which in incorporated by reference herein.

In a preferred embodiment the phenoxide catalyst compound comprises oneor more of:

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

bis(N-ethyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

bis(N-iso-propyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

bis(N-t-butyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

bis(N-hexyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

bis(N-phenyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

bis(N-methyl-3,5-di-t-butylsalicylimino)zirconium(IV) dibenzyl;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV) dichloride;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV) dipivalate;

bis(N-benzyl-3,5-di-t-butylsalicylimino)titanium(IV) dipivalate;

bis(N-benzyl-3,5-di-t-butylsalicylimino)zirconium(IV)di(bis(dimethylamide));

bis(N-iso-propyl-3,5-di-t-amylsalicylimino)zirconium(IV) dibenzyl;

bis(N-iso-propyl-3,5-di-t-octylsalicylimino)zirconium(IV) dibenzyl;

bis(N-iso-propyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)titanium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)hafnium(IV)dibenzyl;

bis(N-iso-butyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-butyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dichloride;

bis(N-hexyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-phenyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3,5-di-(1′-methylcyclohexyl)lsalicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-t-butylsalicylimino)zirconium(IV) dibenzyl;

bis(N-benzyl-3-triphenylmethylsalicylimino)zirconium(IV) dibenzyl;

bis(N-iso-propyl-3,5-di-trimethylsilylsalicylimino)zirconium(IV)dibenzyl;

bis(N-iso-propyl-3-(phenyl)salicylimino)zirconium(IV) dibenzyl;

bis(N-benzyl-3-(2′,6′-di-iso-propylphenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-(2′,6′-di-phenylphenyl)salicylimino)zirconium(IV)dibenzyl;

bis(N-benzyl-3-t-butyl-5-methoxysalicylimino)zirconium(IV) dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)dichloride;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)zirconium(IV)

di(bis(dimethylamide));bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-dimethylbenzyl)phenoxide)zirconium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-t-amylphenoxide)titanium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-dimethylbenzyl)phenoxide)titanium(IV)dibenzyl;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-dimethylbenzyl)phenoxide)titanium(IV)dichloride;

bis(2-(2H-benzotriazol-2-yl)-4,6-di-(1′,1′-dimethylbenzyl)phenoxide)hafnium(IV)dibenzyl;

(N-phenyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

(N-(2′,6′-di-iso-propylphenyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV)tribenzyl;

(N-(2′,6′-di-iso-propylphenyl-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)titanium(IV)tribenzyl; and(N-(2′,6′-di-iso-propylphenyl)-3,5-di-(1′,1′-dimethylbenzyl)salicylimino)zirconium(IV) trichloride.

D. Additional Catalyst Compounds

The catalyst compositions of the invention may include one or morecomplexes known as transition metal catalysts based on bidentate ligandscontaining pyridine or quinoline moieties, such as those described inU.S. application Ser. No. 09/103,620 filed Jun. 23, 1998, which isherein incorporated by reference.

In one embodiment, these catalyst compounds are represented by theformula:

((Z)XA_(t)(YJ))_(q)MQ_(n)  (IX)

where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, bivalent, or trivalent anion; X and Y are bondedto M; one or more of X and Y are heteroatoms, preferably both X and Yare heteroatoms; Y is contained in a heterocyclic ring J, where Jcomprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbonatoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms,preferably 1 to 50 carbon atoms, preferably Z is a cyclic groupcontaining 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1;when t is 1, A is a bridging group joined to at least one of X, Y or J,preferably X and J; q is 1 or 2; n is an integer from 1 to 4 dependingon the oxidation state of M. In one embodiment, where X is oxygen orsulfur then Z is optional. In another embodiment, where X is nitrogen orphosphorous then Z is present. In an embodiment, Z is preferably an arylgroup, more preferably a substituted aryl group.

It is within the scope of this invention, in one embodiment, thecatalyst compounds include complexes of Ni²⁺ and Pd²⁺ described in thearticles Johnson, et al., “New Pd(II)- and Ni(II)-Based Catalysts forPolymerization of Ethylene and a-Olefins”, J. Am. Chem. Soc. 1995, 117,6414-6415 and Johnson, et al., “Copolymerization of Ethylene andPropylene with Functionalized Vinyl Monomers by Palladium(II)Catalysts”, J. Am. Chem. Soc., 1996, 118, 267-268, and WO 96/23010published Aug. 1, 1996, WO 99/02472, U.S. Pat. Nos. 5,852,145, 5,866,663and 5,880,241, which are all herein fully incorporated by reference.These complexes can be either dialkyl ether adducts, or alkylatedreaction products of the described dihalide complexes that can beactivated to a cationic state by the activators of this inventiondescribed below.

Other catalyst compounds include those nickel complexes described in WO99/50313, which is incorporated herein by reference.

Also included are those diimine based ligands of Group 8 to 10 metalcatalyst compounds disclosed in PCT publications WO 96/23010 and WO97/48735 and Gibson, et al., Chem. Comm., pp. 849-850 (1998), all ofwhich are herein incorporated by reference.

Other useful catalyst compounds are those Group 5 and 6 metal imidocomplexes described in EP-A2-0 816 384 and U.S. Pat. No. 5,851,945,which is incorporated herein by reference. In addition, metallocenecatalysts include bridged bis(arylamido) Group 4 compounds described byD. H. McConville, et al., in Organometallics 1195, 14, 5478-5480, whichis herein incorporated by reference. In addition, bridged bis(amido)catalyst compounds are described in WO 96/27439, which is hereinincorporated by reference. Other useful catalysts are described asbis(hydroxy aromatic nitrogen ligands) in U.S. Pat. No. 5,852,146, whichis incorporated herein by reference. Other useful catalysts containingone or more Group 15 atoms include those described in WO 98/46651, whichis herein incorporated herein by reference.

E. Conventional Transition Metal Catalysts

In another embodiment, conventional-type transition metal catalysts maybe used in the practice of this invention. Conventional-type transitionmetal catalysts are those traditional Ziegler-Natta, vanadium andPhillips-type catalysts well known in the art. Such as, for exampleZiegler-Natta catalysts as described in Ziegler-Natta Catalysts andPolymerizations, John Boor, Academic Press, New York, 1979. Examples ofconventional-type transition metal catalysts are also discussed in U.S.Pat. Nos. 4,115,639, 4,077,904, 4,482,687, 4,564,605, 4,721,763,4,879,359 and 4,960,741, all of which are herein fully incorporated byreference. The conventional-type transition metal catalyst compoundsthat may be used in the present invention include transition metalcompounds from Groups 3 to 17, preferably 4 to 12, more preferably 4 to6 of the Periodic Table of Elements.

Preferred conventional-type transition metal catalysts may berepresented by the formula: MR_(x), where M is a metal from Groups 3 to17, preferably Group 4 to 6, more preferably Group 4, most preferablytitanium; R is a halogen or a hydrocarbyloxy group; and x is theoxidation state of the metal M. Non-limiting examples of R includealkoxy, phenoxy, bromide, chloride and fluoride. Non-limiting examplesof conventional-type transition metal catalysts where M is titaniuminclude TiCl₄, TiBr₄, Ti(OC₂H₅)₃Cl, Ti(OC₂H₅)Cl₃, Ti(OC₄H₉)₃Cl,Ti(OC₃H₇)₂Cl₂, Ti(OC₂H₅)₂Br₂, TiCl₃·⅓AlCl₃ and Ti(OC₁₂H₂₅)Cl₃.

Conventional-type transition metal catalyst compounds based onmagnesium/titanium electron-donor complexes that are useful in theinvention are described in, for example, U.S. Pat. Nos. 4,302,565 and4,302,566, which are herein fully incorporate by reference. The MgTiCl₆(ethyl acetate)₄ derivative is particularly preferred.

British Patent Application 2,105,355 and U.S. Pat. No. 5,317,036, hereinincorporated by reference, describes various conventional-type vanadiumcatalyst compounds. Non-limiting examples of conventional-type vanadiumcatalyst compounds include vanadyl trihalide, alkoxy halides andalkoxides such as VOCl₃, VOCl₂(OBu) where Bu=butyl and VO(OC₂H₅)₃;vanadium tetra-halide and vanadium alkoxy halides such as VCl₄ andVCl₃(OBu); vanadium and vanadyl acetyl acetonates and chloroacetylacetonates such as V(AcAc)₃ and VOCl₂(AcAc) where (AcAc) is an acetylacetonate. The preferred conventional-type vanadium catalyst compoundsare VOCl₃, VCl₄ and VOCl₂—OR where R is a hydrocarbon radical,preferably a C₁ to C₁₀ aliphatic or aromatic hydrocarbon radical such asethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl,tertiary-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetylacetonates.

Conventional-type chromium catalyst compounds, often referred to asPhillips-type catalysts, suitable for use in the present inventioninclude CrO₃, chromocene, silyl chromate, chromyl chloride (CrO₂Cl₂),chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc)₃), andthe like. Non-limiting examples are disclosed in U.S. Pat. Nos.3,709,853, 3,709,954, 3,231,550, 3,242,099 and 4,077,904, which areherein fully incorporated by reference.

Still other conventional-type transition metal catalyst compounds andcatalyst systems suitable for use in the present invention are disclosedin U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566, 4,376,062, 4,379,758,5,066,737, 5,763,723, 5,849,655, 5,852,144, 5,854,164 and 5,869,585 andpublished EP-A2 0 416 815 A2 and EP-A1 0 420 436, which are all hereinincorporated by reference.

Other catalysts may include cationic catalysts such as AlCl₃, and othercobalt, iron, nickel and palladium catalysts well known in the art. Seefor example U.S. Pat. Nos. 3,487,112, 4,472,559, 4,182,814 and4,689,437, all of which are incorporated herein by reference.

It is also contemplated that other catalysts can be combined with thecatalyst compounds in the catalyst composition of the invention. Forexample, see U.S. Pat. Nos. 4,937,299, 4,935,474, 5,281,679, 5,359,015,5,470,811, and 5,719,241 all of which are herein fully incorporatedherein reference.

It is further contemplated that one or more of the catalyst compoundsdescribed above or catalyst systems may be used in combination with oneor more conventional catalyst compounds or catalyst systems.Non-limiting examples of mixed catalysts and catalyst systems aredescribed in U.S. Pat. Nos. 4,159,965, 4,325,837, 4,701,432, 5,124,418,5,077,255, 5,183,867, 5,391,660, 5,395,810, 5,691,264, 5,723,399 and5,767,031 and PCT Publication WO 96/23010 published Aug. 1, 1996, all ofwhich are herein fully incorporated by reference.

III. Activators and Activation Methods for Catalyst Compounds

The polymerization catalyst compounds, described above, are typicallyactivated in various ways to yield compounds having a vacantcoordination site that will coordinate, insert, and polymerizeolefin(s). For the purposes of this patent specification and appendedclaims, the term “activator” is defined to be any compound which canactivate any one of the catalyst compounds described above by convertingthe neutral catalyst compound to a catalytically active catalystcompound cation. Non-limiting activators, for example, includealumoxanes, aluminum alkyls, ionizing activators, which may be neutralor ionic, and conventional-type cocatalysts.

A. Aluminoxane and Aluminum Alkyl Activators

In one embodiment, alumoxanes activators are utilized as an activator inthe catalyst composition of the invention. Alumoxanes are generallyoligomeric compounds containing —Al(R)—O— subunits, where R is an alkylgroup. Examples of alumoxanes include methylalumoxane (MAO), modifiedmethylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alumoxanesmay be produced by the hydrolysis of the respective trialkylaluminumcompound. MMAO may be produced by the hydrolysis of trimethylalumium anda higher trialkylaluminum such as triisobutylaluminum. MMAO's aregenerally more soluble in aliphatic solvents and more stable duringstorage. There are a variety of methods for preparing alumoxane andmodified alumoxanes, non-limiting examples of which are described inU.S. Pat. No. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529,5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166,5,856,256 and 5,939,346 and European publications EP-A-0 561 476,EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and PCTpublications WO 94/10180 and WO 99/15534, all of which are herein fullyincorporated by reference. A another alumoxane is a modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available from AkzoChemicals, Inc. under the trade name Modified Methylalumoxane type 3A,covered under patent number U.S. Pat. No. 5,041,584).

Aluminum Alkyl or organoaluminum compounds which may be utilized asactivators include trimethylalumium, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and thelike.

B. Ionizing Activators

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl)boron, a trisperfluorophenyl boronmetalloid precursor or a trisperfluoronaphtyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459) or combination thereof. It is also within the scope ofthis invention to use neutral or ionic activators alone or incombination with alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium and indium or mixtures thereof. Thethree substituent groups are each independently selected from alkyls,alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20carbon atoms (including substituted aryls). More preferably, the threegroups are alkyls having 1 to 4 carbon groups, phenyl, napthyl ormixtures thereof. Even more preferably, the three groups arehalogenated, preferably fluorinated, aryl groups. Most preferably, theneutral stoichiometric activator is trisperfluorophenyl boron ortrisperfluoronapthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:

(L-H)_(d) ⁺(A^(d−))  (X)

wherein L is an neutral Lewis base;

H is hydrogen;

(L-H)⁺ is a Bronsted acid

A^(d−) is a non-coordinating anion having the charge d−

is an integer from 1 to 3.

The cation component, (L-H)_(d) ⁺ may include Bronsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an akyl or aryl, from thebulky ligand metallocene or Group 15 containing transition metalcatalyst precursor, resulting in a cationic transition metal species.

The activating cation (L-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the transition metal catalytic precursor resultingin a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene andmixtures thereof. The activating cation (L-H)_(d) ⁺ may also be anabstracting moiety such as silver, carboniums, tropylium, carbeniums,ferroceniums and mixtures, preferably carboniums and ferroceniums. Mostpreferably (L-H)_(d) ⁺ is triphenyl carbonium.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2-6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than 1occurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable A^(d−) also include diboron compoundsas disclosed in U.S. Pat. No. 5,447,895, which is fully incorporatedherein by reference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention are tri-substituted ammonium salts such as:

trimethylammonium tetraphenylborate,

triethylammonium tetraphenylborate,

tripropylammonium tetraphenylborate,

tri(n-butyl)ammonium tetraphenylborate,

tri(t-butyl)ammonium tetraphenylborate,

N,N-dimethylanilinium tetraphenylborate,

N,N-diethylanilinium tetraphenylborate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,

trimethylammonium tetrakis(pentafluorophenyl)borate,

triethylammonium tetrakis(pentafluorophenyl)borate,

tripropylammonium tetrakis(pentafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,

trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate,

triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate,

dimethyl(t-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,

N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl)borate, and

N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;

dialkyl ammonium salts such as: di-(i-propyl)ammoniumtetrakis(pentafluorophenyl)borate, and dicyclohexylammoniumtetrakis(pentafluorophenyl)borate; and tri-substituted phosphonium saltssuch as: triphenylphosphonium tetrakis(pentafluorophenyl)borate,tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate, andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.

Most preferably, the ionic stoichiometric activator (L-H)_(d) ⁺ (A^(d−))is N,N-dimethylanilinium tetra(perfluorophenyl)borate ortriphenylcarbenium tetra(perfluorophenyl)borate.

In one embodiment, an activation method using ionizing ionic compoundsnot containing an active proton but capable of producing a bulky ligandmetallocene catalyst cation and their non-coordinating anion are alsocontemplated, and are described in EP-A-0 426 637, EP-A-0 573 403 andU.S. Pat. No. 5,387,568, which are all herein incorporated by reference.

C. Conventional-Type Cocatalysts

Typically, conventional transition metal catalyst compounds excludingsome conventional-type chromium catalyst compounds are activated withone or more of the conventional cocatalysts which may be represented bythe formula M³M⁴ _(v)X² _(c)R³ _(b−c), wherein M³ is a metal from Group1 to 3 and 12 to 13 of the Periodic Table of Elements; M⁴ is a metal ofGroup 1 of the Periodic Table of Elements; v is a number from 0 to 1;each X² is any halogen; c is a number from 0 to 3; each R³ is amonovalent hydrocarbon radical or hydrogen; b is a number from 1 to 4;and wherein b minus c is at least 1. Other conventional-typeorganometallic cocatalyst compounds for the above conventional-typetransition metal catalysts have the formula M³R³ _(k), where M³ is aGroup IA, IIA, IIB or IIIA metal, such as lithium, sodium, beryllium,barium, boron, aluminum, zinc, cadmium, and gallium; k equals 1, 2 or 3depending upon the valency of M³ which valency in turn normally dependsupon the particular Group to which M³ belongs; and each R³ may be anymonovalent hydrocarbon radical.

Non-limiting examples of conventional-type organometallic cocatalystcompounds useful with the conventional-type catalyst compounds describedabove include methyllithium, butyllithium, dihexylmercury,butylmagnesium, diethylcadmium, benzylpotassium, diethylzinc,tri-n-butylaluminum, diisobutyl ethylboron, diethylcadmium,di-n-butylzinc and tri-n-amylboron, and, in particular, the aluminumalkyls, such as tri-hexyl-aluminum, triethylaluminum, trimethylalumium,and tri-isobutylaluminum. Other conventional-type cocatalyst compoundsinclude monoorganohalides and hydrides of Group 2 metals, and mono- ordi-organohalides and hydrides of Group 3 and 13 metals. Non-limitingexamples of such conventional-type cocatalyst compounds includedi-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesiumchloride, ethylberyllium chloride, ethylcalcium bromide, diisobutylaluminum hydride, methylcadmium hydride, diethylboron hydride,hexylberyllium hydride, dipropylboron hydride, octylmagnesium hydride,butylzinc hydride, dichloroboron hydride, di-bromo-aluminum hydride andbromocadmium hydride. Conventional-type organometallic cocatalystcompounds are known to those in the art and a more complete discussionof these compounds may be found in U.S. Pat. Nos. 3,221,002 and5,093,415, which are herein fully incorporated by reference.

D. Additional Activators

Other activators include those described in PCT publication WO 98/07515such as tris(2,2′,2″-nonafluorobiphenyl)fluoroaluminate, whichpublication is fully incorporated herein by reference. Combinations ofactivators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example,EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044 and U.S.Pat. Nos. 5,153,157 and 5,453,410 all of which are herein fullyincorporated by reference.

Other suitable activators are disclosed in WO 98/09996, incorporatedherein by reference, which describes activating bulky ligand metallocenecatalyst compounds with perchlorates, periodates and iodates includingtheir hydrates. WO 98/30602 and WO 98/30603, incorporated by reference,describe the use of lithium (2,2′-bisphenyl-ditrimethylsilicate)·4THF asan activator for a bulky ligand metallocene catalyst compound. WO99/18135, incorporated herein by reference, describes the use oforganoboron-aluminum acitivators. EP-B1-0 781 299 describes using asilylium salt in combination with a non-coordinating compatible anion.Also, methods of activation such as using radiation (see EP-B1-0 615 981herein incorporated by reference), electrochemical oxidation, and thelike are also contemplated as activating methods for the purposes ofrendering the neutral bulky ligand metallocene catalyst compound orprecursor to a bulky ligand metallocene cation capable of polymerizingolefins. Other activators or methods for activating a bulky ligandmetallocene catalyst compound are described in for example, U.S. Pat.Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO 99/42467(dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)benzimidazolide),which are herein incorporated by reference.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula: (OX^(e+))_(d)(A^(d−))_(e) wherein: OX^(e+)is a cationic oxidizing agent having a charge of e+; e is an integerfrom 1 to 3; and A⁻, and d are as previously defined. Examples ofcationic oxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb⁺². Preferred embodiments of A^(d−) are thoseanions previously defined with respect to the Bronsted acid containingactivators, especially tetrakis(pentafluorophenyl)borate.

It within the scope of this invention that catalyst compounds can becombined one or more activators or activation methods described above.For example, a combination of activators have been described in U.S.Pat. Nos. 5,153,157 and 5,453,410, European publication EP-B1 0 573 120,and PCT publications WO 94/07928 and WO 95/14044. These documents alldiscuss the use of an alumoxane and an ionizing activator with a bulkyligand metallocene catalyst compound.

IV. Supports, Carriers and General Supporting Techniques

The catalyst composition of the invention includes a support material orcarrier, and preferably includes a supported activator. For example, thecatalyst composition component, preferably the activator compound and/orthe catalyst compound, is deposited on, contacted with, vaporized with,bonded to, or incorporated within, adsorbed or absorbed in, or on, asupport or carrier.

A. Support Material

The support material is any of the conventional support materials.Preferably the supported material is a porous support material, forexample, talc, inorganic oxides and inorganic chlorides. Other supportmaterials include resinous support materials such as polystyrene,functionalized or crosslinked organic supports, such as polystyrenedivinyl benzene polyolefins or polymeric compounds, zeolites, clays, orany other organic or inorganic support material and the like, ormixtures thereof.

The preferred support materials are inorganic oxides that include thoseGroup 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports includesilica, fumed silica, alumina (WO 99/60033), silica-alumina and mixturesthereof. Other useful supports include magnesia, titania, zirconia,magnesium chloride (U.S. Pat. No. 5,965,477), montmorillonite (EuropeanPat. EP-B1 0 511 665), phyllosilicate, zeolites, talc, clays (U.S. Pat.No. 6,034,187) and the like. Also, combinations of these supportmaterials may be used, for example, silica-chromium, silica-alumina,silica-titania and the like. Additional support materials may includethose porous acrylic polymers described in EP 0 767 184 B1, which isincorporated herein by reference. Other support materials includenanocomposites as described in PCT WO 99/47598, aerogels as described inWO 99/48605, spherulites as described in U.S. Pat. No. 5,972,510 andpolymeric beads as described in WO 99/50311, which are all hereinincorporated by reference. A preferred support is fumed silica availableunder the trade name Cabosil™ TS-610, available from Cabot Corporation.Fumed silica is typically a silica with particles 7 to 30 nanometers insize that has been treated with dimethylsilyldichloride such that amajority of the surface hydroxyl groups are capped.

It is preferred that the support material, most preferably an inorganicoxide, has a surface area in the range of from about 10 to about 700m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g andaverage particle size in the range of from about 5 to about 500 μm. Morepreferably, the surface area of the support material is in the range offrom about 50 to about 500 m²/g, pore volume of from about 0.5 to about3.5 cc/g and average particle size of from about 10 to about 200 μm.Most preferably the surface area of the support material is in the rangeis from about 100 to about 400 m²/g, pore volume from about 0.8 to about3.0 cc/g and average particle size, is from about 5 to about 100 μm. Theaverage pore size of the carrier of the invention typically has poresize in the range of from 10 to 1000 Å, preferably 50 to about 500 Å,and most preferably 75 to about 350 Å.

The support materials may be treated chemically, for example with afluoride compound as described in WO 00/12565, which is hereinincorporated by reference. Other supported activators are described infor example WO 00/13792 that refers to supported boron containing solidacid complex.

In a preferred method of forming a supported catalyst compositioncomponent, the amount of liquid in which the activator is present is inan amount that is less than four times the pore volume of the supportmaterial, more preferably less than three times, even more preferablyless than two times; preferred ranges being from 1.1 times to 3.5 timesrange and most preferably in the 1.2 to 3 times range. In an alternativeembodiment, the amount of liquid in which the activator is present isfrom one to less than one times the pore volume of the support materialutilized in forming the supported activator.

Procedures for measuring the total pore volume of a porous support arewell known in the art. Details of one of these procedures is discussedin Volume 1, Experimental Methods in Catalytic Research (Academic Press,1968) (specifically see pages 67-96). This preferred procedure involvesthe use of a classical BET apparatus for nitrogen absorption. Anothermethod well known in the art is described in Innes, Total Porosity andParticle Density of Fluid Catalysts By Liquid Titration, Vol. 28, No. 3,Analytical Chemistry 332-334 (March, 1956).

B. Supported Activators

In one embodiment, the catalyst composition includes a supportedactivator. Many supported activators are described in various patentsand publications which include: U.S. Pat. No. 5,728,855 directed to theforming a supported oligomeric alkylaluminoxane formed by treating atrialkylaluminum with carbon dioxide prior to hydrolysis; U.S. Pat. Nos.5,831,109 and 5,777,143 discusses a supported methylalumoxane made usinga non-hydrolytic process; U.S. Pat. No. 5,731,451 relates to a processfor making a supported alumoxane by oxygenation with a trialkylsiloxymoiety; U.S. Pat. No. 5,856,255 discusses forming a supported auxiliarycatalyst (alumoxane or organoboron compound) at elevated temperaturesand pressures; U.S. Pat. No. 5,739,368 discusses a process of heattreating alumoxane and placing it on a support; EP-A-0 545 152 relatesto adding a metallocene to a supported alumoxane and adding moremethylalumoxane; U.S. Pat. Nos. 5,756,416 and 6,028,151 discuss acatalyst composition of a alumoxane impregnated support and ametallocene and a bulky aluminum alkyl and methylalumoxane; EP-B1-0 662979 discusses the use of a metallocene with a catalyst support of silicareacted with alumoxane; PCT WO 96/16092 relates to a heated supporttreated with alumoxane and washing to remove unfixed alumoxane; U.S.Pat. Nos. 4,912,075, 4,937,301, 5,008,228, 5,086,025, 5,147,949,4,871,705, 5,229,478, 4,935,397, 4,937,217 and 5,057,475, and PCT WO94/26793 all directed to adding a metallocene to a supported activator;U.S. Pat. No. 5,902,766 relates to a supported activator having aspecified distribution of alumoxane on the silica particles; U.S. Pat.No. 5,468,702 relates to aging a supported activator and adding ametallocene; U.S. Pat. No. 5,968,864 discusses treating a solid withalumoxane and introducing a metallocene; EP 0 747 430 A1 relates to aprocess using a metallocene on a supported methylalumoxane andtrimethylalumium; EP 0 969 019 A1 discusses the use of a metallocene anda supported activator; EP-B2-0 170 059 relates to a polymerizationprocess using a metallocene and a organo-aluminuim compound, which isformed by reacting aluminum trialkyl with a water containing support;U.S. Pat. No. 5,212,232 discusses the use of a supported alumoxane and ametallocene for producing styrene based polymers; U.S. Pat. No.5,026,797 discusses a polymerization process using a solid component ofa zirconium compound and a water-insoluble porous inorganic oxidepreliminarily treated with alumoxane; U.S. Pat. No. 5,910,463 relates toa process for preparing a catalyst support by combining a dehydratedsupport material, an alumoxane and a polyfunctional organic crosslinker;U.S. Pat. Nos. 5,332,706, 5,473,028, 5,602,067 and 5,420,220 discusses aprocess for making a supported activator where the volume of alumoxanesolution is less than the pore volume of the support material; WO98/02246 discusses silica treated with a solution containing a source ofaluminum and a metallocene; WO 99/03580 relates to the use of asupported alumoxane and a metallocene; EP-A1-0 953 581 discloses aheterogeneous catalytic system of a supported alumoxane and ametallocene; U.S. Pat. No. 5,015,749 discusses a process for preparing apolyhydrocarbyl-alumoxane using a porous organic or inorganic imbibermaterial; U.S. Pat. Nos. 5,446,001 and 5,534,474 relates to a processfor preparing one or more alkylaluminoxanes immobilized on a solid,particulate inert support; and EP-A1-0 819 706 relates to a process forpreparing a solid silica treated with alumoxane. Also, the followingarticles, also fully incorporated herein by reference for purposes ofdisclosing useful supported activators and methods for theirpreparation, include: W. Kaminsky, et al., “Polymerization of Styrenewith Supported Half-Sandwich Complexes”, Journal of Polymer Science Vol.37, 2959-2968 (1999) describes a process of adsorbing a methylalumoxaneto a support followed by the adsorption of a metallocene; Junting Xu, etal. “Characterization of isotactic polypropylene prepared withdimethylsilyl bis(1-indenyl)zirconium dichloride supported onmethylaluminoxane pretreated silica”, European Polymer Journal 35 (1999)1289-1294, discusses the use of silica treated with methylalumoxane anda metallocene; Stephen O'Brien, et al., “EXAFS analysis of a chiralalkene polymerization catalyst incorporated in the mesoporous silicateMCM-41” Chem. Commun. 1905-1906 (1997) discloses an immobilizedalumoxane on a modified mesoporous silica; and F. Bonini, et al.,“Propylene Polymerization through Supported Metallocene/MAO Catalysts:Kinetic Analysis and Modeling” Journal of Polymer Science, Vol. 332393-2402 (1995) discusses using a methylalumoxane supported silica witha metallocene. Any of the methods discussed in these references areuseful for producing the supported activator component utilized in thecatalyst composition of the invention and all are incorporated herein byreference.

In another embodiment, the supported activator, such as supportedalumoxane, is aged for a period of time prior to use herein. Forreference please refer to U.S. Pat. Nos. 5,468,702 and 5,602,217,incorporated herein by reference.

In an embodiment, the supported activator is in a dried state or asolid. In another embodiment, the supported activator is in asubstantially dry state or a slurry, preferably in a mineral oil slurry.

In another embodiment, two or more separately supported activators areused, or alternatively, two or more different activators on a singlesupport are used.

In another embodiment, the support material, preferably partially ortotally dehydrated support material, preferably 200° C. to 600° C.dehydrated silica, is then contacted with an organoaluminum or alumoxanecompound. Preferably in an embodiment where an organoaluminum compoundis used, the activator is formed in situ on and in the support materialas a result of the reaction of, for example, trimethylalumium and water.

In another embodiment, Lewis base-containing supports are reacted with aLewis acidic activator to form a support bonded Lewis acid compound. TheLewis base hydroxyl groups of silica are exemplary of metal/metalloidoxides where this method of bonding to a support occurs. This embodimentis described in U.S. patent application Ser. No. 09/191,922, filed Nov.13, 1998, which is herein incorporated by reference.

Other embodiments of supporting an activator are described in U.S. Pat.No. 5,427,991, where supported non-coordinating anions derived fromtrisperfluorophenyl boron are described; U.S. Pat. No. 5,643,847discusses the reaction of Group 13 Lewis acid compounds with metaloxides such as silica and illustrates the reaction oftrisperfluorophenyl boron with silanol groups (the hydroxyl groups ofsilicon) resulting in bound anions capable of protonating transitionmetal organometallic catalyst compounds to form catalytically activecations counter-balanced by the bound anions; immobilized Group IIIALewis acid catalysts suitable for carbocationic polymerizations aredescribed in U.S. Pat. No. 5,288,677; and James C. W. Chien, Jour. Poly.Sci.: Pt A: Poly. Chem, Vol. 29, 1603-1607 (1991), describes the olefinpolymerization utility of methylalumoxane (MAO) reacted with silica(SiO₂) and metallocenes and describes a covalent bonding of the aluminumatom to the silica through an oxygen atom in the surface hydroxyl groupsof the silica.

In a preferred embodiment, a supported activator is formed by preparingin an agitated, and temperature and pressure controlled vessel asolution of the activator and a suitable solvent, then adding thesupport material at temperatures from 0° C. to 100° C., contacting thesupport with the activator solution for up to 24 hours, then using acombination of heat and pressure to remove the solvent to produce a freeflowing powder. Temperatures can range from 40 to 120° C. and pressuresfrom 5 psia to 20 psia (34.5 to 138 kPa). An inert gas sweep can also beused in assist in removing solvent. Alternate orders of addition, suchas slurrying the support material in an appropriate solvent then addingthe activator, can be used.

C. Spray Dried Catalyst Composition Components

In another embodiment a support is combined with one or more activatorsand is spray dried to form a supported activator. In a preferredembodiment, fumed silica is combined with methyl alumoxane and thenspray dried to from supported methyl alumoxane. Preferably a support iscombined with alumoxane, spray dried and then placed in mineral oil toform a slurry useful in the instant invention.

In another embodiment, the catalyst compounds described above have beencombined with optional support material(s) and or optional activator(s)and spray dried prior to being combined with the slurry diluent.

In another embodiment, the catalyst compounds and/or the activators arepreferably combined with a support material such as a particulate fillermaterial and then spray dried, preferably to form a free flowing powder.Spray drying may be by any means known in the art. Please see EP A 0 668295 B1, U.S. Pat. No. 5,674,795 and U.S. Pat. No. 5,672,669 and U.S.patent application Ser. No. 09/464,114 filed Dec. 16, 1999, whichparticularly describe spray drying of supported catalysts. In generalone may spray dry the catalysts by placing the catalyst compound and theoptional activator in solution (allowing the catalyst compound andactivator to react, if desired), adding a filler material such as silicaor fumed silica, such as Gasil™ or Cabosil™, then forcing the solutionat high pressures through a nozzle. The solution may be sprayed onto asurface or sprayed such that the droplets dry in midair. The methodgenerally employed is to disperse the silica in toluene, stir in theactivator solution, and then stir in the catalyst compound solution.Typical slurry concentrations are about 5 to 8 wt %. This formulationmay sit as a slurry for as long as 30 minutes with mild stirring ormanual shaking to keep it as a suspension before spray-drying. In onepreferred embodiment, the makeup of the dried material is about 40-50 wt% activator (preferably alumoxane), 50-60 SiO₂ and about ˜2 wt %catalyst compound.

For simple catalyst compound mixtures, the two or more catalystcompounds can be added together in the desired ratio in the last step.In another embodiment, more complex procedures are possible, such asaddition of a first catalyst compound to the activator/filler mixturefor a specified reaction time t, followed by the addition of the secondcatalyst compound solution, mixed for another specified time x, afterwhich the mixture is cosprayed. Lastly, another additive, such as1-hexene in about 10 vol % can be present in the activator/fillermixture prior to the addition of the first metal catalyst compound.

In another embodiment binders are added to the mix. These can be addedas a means of improving the particle morphology, i.e. narrowing theparticle size distribution, lower porosity of the particles and allowingfor a reduced quantity of alumoxane, which is acting as the ‘binder’.

In another embodiment a solution of a bulky ligand metallocene compoundand optional activator can be combined with a different slurried spraydried catalyst compound and then introduced into a reactor.

The spray dried particles are generally fed into the polymerizationreactor as a mineral oil slurry. Solids concentrations in oil are about10 to 30 weight %, preferably 15 to 25 weight %. In some embodiments,the spray dried particles can be from less than about 10 micrometers insize up to about 100 micrometers, compared to conventional supportedcatalysts which are about 50 micrometers. In a preferred embodiment thesupport has an average particle size of 1 to 50 microns, preferably 10to 40 microns.

V. Catalyst Compositions of the Invention

To prepare the catalyst composition of the invention, the catalystcomponents described above are utilized in a catalyst component slurryand/or in a catalyst component solution. For the purposes of thisinvention, a slurry is defined to be a suspension of a solid, where thesolid may or may not be porous, in a liquid. The catalyst componentslurry and the catalyst component solution are combined to form thecatalyst composition which is then introduced into a polymerizationreactor.

A. Catalyst Component Slurry

In one embodiment, the catalyst component slurry includes an activatorand a support, or a supported activator. In another embodiment, theslurry also includes a catalyst compound in addition to the activatorand the support and/or the supported activator. In one embodiment, thecatalyst compound in the slurry is supported.

In another embodiment, the slurry includes one or more activator(s) andsupport(s) and/or supported activator(s) and/or one more catalystcompound(s). For example, the slurry may include two or more activators(such as a supported alumoxane and a modified alumoxane) and a catalystcompound, or the slurry may include a supported activator and more thanone catalyst compounds. Preferably, the slurry comprises a supportedactivator and two catalyst compounds.

In another embodiment the slurry comprises supported activator and twodifferent catalyst compounds, which may be added to the slurryseparately or in combination.

In another embodiment the slurry, containing a supported alumoxane, iscontacted with a catalyst compound, allowed to react, and thereafter theslurry is contacted with another catalyst compound. In anotherembodiment the slurry containing a supported alumoxane is contacted withtwo catalyst compounds at the same time, and allowed to react.

In another embodiment the molar ratio of metal in the activator to metalin the catalyst compound in the slurry is 1000:1 to 0.5:1, preferably300:1 to 1:1, more preferably 150:1 to 1:1.

In another embodiment the slurry contains a support material which maybe any inert particulate carrier material known in the art, including,but not limited to, silica, fumed silica, alumina, clay, talc or othersupport materials such as disclosed above. In a preferred embodiment,the slurry contains a supported activator, such as those disclosedabove, preferably methyl alumoxane and/or modified methyl alumoxane on asupport of silica.

The catalyst component slurry used in the process of this invention istypically prepared by suspending the catalyst components, preferably thesupport, the activator and optional catalyst compounds in a liquiddiluent. The liquid diluent is typically an alkane having from 3 to 60carbon atoms, preferably having from 5 to 20 carbon atoms, preferably abranched alkane, or an organic composition such as mineral oil orsilicone oil. The diluent employed is preferably liquid under theconditions of polymerization and relatively inert. The concentration ofthe components in the slurry is controlled such that a desired ratio ofcatalyst compound(s) to activator, and/or catalyst compound to catalystcompound is fed into the reactor.

Typically, the catalyst compound and the support and activator, orsupported activator, and the slurry diluent are allowed to contact eachother for a time sufficient for at least 50% of the catalyst compoundsto be deposited into or on the support, preferably at least 70%,preferably at least 75%, preferably at least 80%, more preferably atleast 90%, preferably at least 95%, preferably at least 99%. In anembodiment, the catalyst component slurry is prepared prior to its usein the catalyst feed system of the invention. Times allowed for mixingare up to 10 hours, typically up to 6 hours, more typically 4 to 6hours. In one embodiment of this invention a catalyst compound will beconsidered to be in or on the support if the concentration of thecatalyst compound in the liquid portion of the slurry is reduced overtime after adding the catalyst compound to the slurry. Concentration ofthe catalyst compound in the liquid diluent may be measured for example,by inductively coupled plasma spectroscopy (ICPS), or by ultraviolet(UV) spectroscopy, after standardization with a calibration curveprepared at the appropriate concentration range, as is known in the art.Thus for example, 70% of a catalyst compound will be considered to havedeposited in or on a support if the concentration of the catalystcompound in the liquid (not including the support) is reduced by 70%from its initial concentration.

In one embodiment, the catalyst compounds can be added to the slurry asa solution, slurry, or powder. The catalyst component slurry is preparedprior to its use in the polymerization process of the invention or thecatalyst component slurry may be prepared in-line.

In one embodiment, the slurry is prepared by combining the catalystcomponents, such as for example the catalyst or supported catalyst andthe support and activator or supported activator, all at once. Inanother embodiment, the slurry is prepared by first adding a supportmaterial, then adding the combination of a catalyst and an activatorcomponent.

In another embodiment the slurry comprises a supported activator and atleast one catalyst compound where the catalyst compound is combined withthe slurry as a solution. A preferred solvent is mineral oil.

In a another embodiment, alumoxane, preferably methyl alumoxane ormodified methyl alumoxane, is combined with a support such as calcinedsilica or fumed silica to form a supported activator, the supportedactivator is then dispersed in a liquid, such as degassed mineral oil,and then one or more catalyst compounds are added to the dispersion andmixed to form the catalyst component slurry. The catalyst compounds arepreferably added to the dispersion as a solid, powder, solution or aslurry, preferably a slurry of mineral oil. If more than one catalystcompound is added to the dispersion, the catalyst compounds can be addedsequentially, or at the same time.

In another embodiment the catalyst compound is added to the slurry insolid or powder form. In a preferred embodiment, a Group 15 containingcatalyst compound is added to the slurry in powder or solid form. Inanother preferred embodiment, [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ and or[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂ is added to the slurry as a powder.

In a preferred embodiment the catalyst component slurry comprisesmineral oil and has a viscosity of about 130 to about 2000 cP at 20° C.,more preferably about 180 to about 1500 cP at 20° C. and even morepreferably about 200 to about 800 cP at 20° C. as measured with aBrookfield model LVDV-III Rheometer housed in a nitrogen purged drybox(in such a manner that the atmosphere is substantially free of moistureand oxygen, i.e. less than several ppmv of each). The catalyst componentslurries are made in a nitrogen purged drybox, and rolled in theirclosed glass containers until immediately before the viscositymeasurements are made, in order to ensure that they are fully suspendedat the start of the trial. Temperature of the viscometer is controlledvia an external temperature bath circulating heat transfer fluid intothe viscometer. The rheometer was fitted with the appropriate spindlefor the test material as specified in the unit's application guide.Typically, a SC4-34 or SC4-25 spindle was used. Data analysis wasperformed using Rheocalc V1.1 software, copyright 1995, BrookfieldEngineering Laboratories, preferably purchased and used with the unit.

In one embodiment, the catalyst component slurry comprises a supportedactivator and one or more or a combination of the catalyst compound(s)described in Formula I to IX above.

In another embodiment, the catalyst component slurry comprises asupported activator and one or more or a combination of the Group 15catalyst compound(s) represented by Formula I or II described above.

In another embodiment, the catalyst component slurry comprises asupported activator and one or more or combination of the bulky ligandcatalyst compound(s) represented by Formula III to VI described above.

In another embodiment, the slurry comprises supported activator, a Group15 catalyst compound(s) represented by Formula I or II described above,and a the bulky ligand catalyst compound(s) represented by Formula IIIto VI

In another embodiment, the slurry comprises supported alumoxane and[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH MBz₂ where M is a Group 4 metal, each Bz isa independently a benzyl group and Me is methyl.

In another embodiment, the slurry comprises a supported alumoxane, aGroup 15 catalysts compound and one of the following:bis(n-propylcyclopentadienyl)-MX₂,(pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂,bis(indenyl)-MX₂, or(tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂, where M iszirconium, hafnium or titanium and X is chlorine, bromine, or fluorine.

In the polymerization process of the invention, described below, any ofthe above described catalyst component containing slurries may becombined with any of the catalyst component containing solutionsdescribed below. In addition, more than one catalyst componentcontaining slurry may be utilized.

B. Catalyst Component Solution

In one embodiment, the catalyst component solution includes a catalystcompound. In another embodiment, the solution also includes an activatorin addition to the catalyst compound.

The solution used in the process of this invention is typically preparedby dissolving the catalyst compound and optional activators in a liquidsolvent. The liquid solvent is typically an alkane, such as a C₅ to C₃₀alkane, preferably a C₅ to C₁₀ alkane. Cyclic alkanes such ascyclohexane and aromatic compounds such as toluene may also be used. Inaddition, mineral oil may be used as a solvent. The solution employedshould be liquid under the conditions of polymerization and relativelyinert. In one embodiment, the liquid utilized in the catalyst compoundsolution is different from the diluent used in the catalyst componentslurry. In another embodiment, the liquid utilized in the catalystcompound solution is the same as the diluent used in the catalystcomponent solution.

In a preferred embodiment the ratio of metal in the activator to metalin the catalyst compound in the solution is 1000:1 to 0.5:1, preferably300:1 to 1:1, more preferably 150:1 to 1:1.

In a preferred embodiment, the activator and catalyst compound ispresent in the solution at up to about 90 wt %, preferably at up toabout 50 wt %, preferably at up to about 20 wt %, preferably at up toabout 10 wt %, more preferably at up to about 5 wt % , more preferablyat less than 1 wt %, more preferably between 100 ppm and 1 wt % basedupon the weight of the solvent and the activator or catalyst compound.

In one embodiment, the catalyst component solution comprises any one ofthe catalyst compounds described in Formula I to IX above.

In another embodiment, the catalyst component solution comprises a Groupcatalyst compound represented by Formula I or II described above.

In another embodiment, the catalyst component solution comprises a bulkyligand catalyst compound represented by Formula III to VI describedabove.

In a preferred embodiment the solution comprisesbis(n-propylcyclopentadienyl)-MX₂,(pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂,bis(indenyl)-MX₂,(tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂, where M is aGroup 4 metal, preferably zirconium, hafnium or titanium and X ischlorine, bromine, or fluorine.

In the polymerization process of the invention, described below, any ofthe above described catalyst component containing solution(s) may becombined with any of the catalyst component containing slurry/slurriesdescribed above. In addition, more than one catalyst componentcontaining solution may be utilized.

C. Catalyst Compositions

The catalyst composition of the invention is formed by combining any oneof the catalyst component slurries with any one of the catalystcomponent solutions described above. Generally, the catalyst componentslurry and the catalyst component solution are mixed in the process ofthe invention to form the final catalyst composition, which is thenintroduced into a polymerization reactor and combined with and one ormore olefins.

In one embodiment, the slurry contains at least one support and at leastone activator, preferably a supported activator, and the solutioncontains at least one catalyst compound.

In another embodiment, the catalyst component slurry contains a support,and an activator and/or a supported activator, and the catalystcomponent solution contains at least one catalyst compound and at leastone activator.

In one embodiment, the slurry contains at least one support and at leastone activator, preferably a supported activator, and the solutioncontains one or more catalyst compound(s) and/or one or more activatorcompound(s).

In another embodiment, the catalyst component slurry contains more thanone support(s), activator(s) and/or supported activator(s), and thecatalyst component solution contains at least one catalyst compound.

In another embodiment, the catalyst component slurry contains more thanone support(s), activator(s) and/or supported activator(s), and thecatalyst component solution contains at least one catalyst compound andat least one activator.

In another embodiment, the catalyst component slurry contains more thanone support(s), activator(s) and/or supported activator(s), and thecatalyst component solution contains one or more catalyst compound(s)and/or one or more activator compound(s).

In another embodiment, the catalyst component slurry contains a support,an activator and/or a supported activator, and also contains a catalystcompound and/or a supported catalyst compound, and the catalystcomponent solution contains at least one catalyst compound.

In another embodiment, the catalyst component slurry contains a support,an activator and/or a supported activator, and also contains a catalystcompound and/or a supported catalyst compound, and the catalystcomponent solution contains at least one catalyst compound and at leastone activator.

In another embodiment, the catalyst component slurry contains a support,an activator and/or a supported activator, and also contains a catalystcompound and/or a supported catalyst compound, and the catalystcomponent solution contains one or more catalyst compound(s) and/or oneor more activator compound(s).

In another embodiment, the catalyst component slurry contains a support,an activator and/or a supported activator and more than one catalystcompound(s) and/or supported catalyst compounds, and the catalystcomponent solution contains at least one catalyst compound.

In another embodiment, the catalyst component slurry contains a support,an activator and/or a supported activator and more than one catalystcompound(s) and/or supported catalyst compounds, and the catalystcomponent solution contains at least one catalyst compound and at leastone activator.

In another embodiment, the catalyst component slurry contains a support,an activator and/or a supported activator and more than one catalystcompound(s) and/or supported catalyst compounds, and the catalystcomponent solution contains one or more catalyst compound(s) and/or oneor more activator compound(s).

In another embodiment, the catalyst component slurry contains more thanone support(s), activator(s) and/or supported activators and more thanone catalyst compound(s) and/or supported catalyst compound(s), and thecatalyst component solution contains at least one catalyst compound.

In another embodiment, the catalyst component slurry contains more thanone support(s), activator(s) and/or supported activators and more thanone catalyst compound(s) and/or supported catalyst compound(s), and thecatalyst component solution contains at least one catalyst compound andat least one activator.

In another embodiment, the catalyst component slurry contains more thanone support(s), activator(s) and/or supported activators and more thanone catalyst compound(s) and/or supported catalyst compound(s), and thecatalyst component solution contains one or more catalyst compound(s)and/or one or more activator compound(s).

In one embodiment the catalyst composition, formed by combining thecatalyst component slurry and the catalyst component solution, has aviscosity of about 130 to about 2000 cP at 20° C., more preferably about180 to about 1500 cP at 20° C. even more preferably about 200 to about800 cP at 20° C.

In another embodiment, the catalyst component solution comprises, up to80 weight %, preferably up to 50 weight %, preferably up to 20 weight %,preferably up to 15 weight %, more preferably between 1 to 10 weight %,more preferably 3 to 8 weight % of the combination of the catalystcomponent solution and the catalyst component slurry, based upon theweight of the solution and the slurry. In another preferred embodiment,the catalyst component solution comprises mineral oil and comprises upto 90 weight %, preferably up to 80 weight %, more preferably between 1to 50 weight %, and more preferably 1 to 20 weight % of the combinationof the catalyst component solution and the catalyst component slurry,based upon the weight of the solution and the slurry.

In one embodiment, the catalyst component slurry is fed to thepolymerization reactor utilizing a slurry feeder. In another embodimentthe catalyst composition is fed to the polymerization reactor utilizinga slurry feeder. A slurry feeder, for example, is described U.S. Pat.No. 5,674,795, incorporated herein by reference.

In one embodiment, the catalyst component solution, comprising acatalyst compound, is contacted with the catalyst component slurry sothat at least 50% of the catalyst compound originally in the catalystcomponent solution is deposited in or on the support, preferably atleast 70%, preferably at least 75%, preferably at least 80%, morepreferably at least 90%, preferably at least 95%, preferably at least99%.

In another embodiment, the catalyst component solution comprising ametallocene catalyst compound, is contacted with a catalyst componentslurry comprising a support and an activator, preferably a supportedactivator, to form an immobilized catalyst composition. Aftercontacting, all or substantially all, preferably at least 50% preferablyat least 70%, preferably at least 75%, preferably at least 80%, morepreferably at least 90%, preferably at least 95%, preferably at least99% of the catalyst compound from the catalyst component solution isdeposited in or on the support initially contained in the catalystcomponent slurry. In one embodiment, a catalyst compound will beconsidered to be in or on the support if the concentration of thecatalyst compound in the liquid portion of the combination is reducedover time after adding the catalyst compound from the solution. Thecatalyst concentration may be measured as described above.

In another embodiment, the supported activator is in a mineral oil thatis then contacted with a metallocene catalyst solution prior tointroducing the catalyst composition to the reactor, preferably wherethe contacting takes place in-line.

In another embodiment, the immobilized catalyst composition system orcomponents thereof may be contacted with a carboxylate metal salt asdescribed in PCT publication WO 00/02930 and WO 00/0293 1, which areherein incorporated by reference.

In another embodiment the solution comprises a catalyst compound and theslurry comprises a supported activator, such as supported alumoxane, andtwo or more catalyst compounds, that may be the same or different fromthe catalyst compound in the solution. The two catalyst compounds may beadded to the slurry before or after the supported activator. In apreferred embodiment the supported activator is added to the liquiddiluent first to form a slurry, then a catalyst compound is added to theslurry, and thereafter another catalyst compound is added to the slurry.The second catalyst is preferably added after the first catalystcompound and the supported activator have been contacted for at least 1minute, preferably at least 15 minutes, more preferably at least 30minutes, more preferably at least 60 minutes, more preferably at least120 minutes, more preferably at least 360 minutes.

In another embodiment the two catalyst compounds are added to the slurryat the same time, in the same or different solutions. In anotherembodiment, a catalyst compound is contacted with an unsupportedactivator prior to being placed in the slurry. In a preferredembodiment, the unsupported activator is a modified or unmodifiedalumoxane, such as methyl alumoxane.

In another embodiment, the catalyst compound may be added to thesolution or slurry in its constituent parts of metal compound andligands. For example, cyclopentadienyl groups such as substituted orunsubstituted cyclopentadiene, indene, fluorene groups and metalcompounds such as zirconium tetrahalide may be added to the slurry orsolution or both and allowed to react therein. Likewise, one may alsoadd metal compounds and or ligands to the solution and or slurry thatalready contains catalyst compounds. The metal compounds and ligands maybe the same or different from the components of the catalyst compound inthe solution or slurry. In another embodiment ligands and/or metalcompounds may be added to both the solution and the slurry.

In another embodiment the catalyst composition comprises a “bisamide”catalyst compound (i.e., a bridged bis(arylamido) Group 4 compoundsdescribed by D. H. McConville, et al., in Organometallics 1195, 14,5478-5480, or a bridged bis(amido) catalyst compounds described in WO96/27439) combined with an activator, spray dried to a powder state,then combined with mineral oil to form a slurry. This combination maythen be combined with various catalyst component solutions to form aparticularly effective multiple catalyst systems. Preferred catalystcompounds include those described above as bulky ligand metallocenecatalysts. In another preferred embodiment the slurry comprises asupported activator and the solution comprises a catalyst compound. Thecatalyst compounds may be selected from various catalyst compoundsdescribed above including bulky ligand metallocenes.

In another embodiment, the slurry comprises[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ or [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂,where each Bz is independently a benzyl group, Me is methyl, and thesolution comprises bis(n-propylcyclopentadienyl)-MX₂,(pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂,bis(indenyl)-MX₂, or (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl) MX₂, where M is zirconium, hafnium ortitanium and X is chlorine, bromine, or fluorine.

In another embodiment, the solution comprises[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ or [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂,where each Bz is independently a benzyl group, Me is methyl, and theslurry comprises: 1) supported alumoxane, and2)bis(n-propylcyclopentadienyl)-MX₂,pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂,bis(indenyl)-MX₂, or(tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂, where M iszirconium, hafnium or titanium and chlorine, bromine, or fluorine.

In another embodiment, the slurry comprises: 1) a supported alumoxane,2)bis(n-propylcyclopentadienyl)-MX₂,(pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)MX₂,bis(indenyl)-MX₂, (tetramethylcyclopentadienyl)(n-propylcyclopentadienyl) MX₂, where M is zirconium, hafnium ortitanium and X is chlorine, bromine, or fluorine, and 3)[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ or [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂,and the solution comprises a bulky ligand metalloc compound.

In another embodiment, the slurry comprises mineral oil and a spraydried catalyst compound. In another embodiment, the spray dried catalystcompound is a Group 15 containing metal compound. In a preferredembodiment, the spray dried catalyst compound comprises[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBZ₂.

In another embodiment, the catalyst compound and the supported activatormay be combined before being combined with the slurry diluent or after.

In another embodiment the solution comprises a catalyst compound ofbis-indenyl zirconium dichloride, bis(n-propylcyclopentadienyl)zirconiumdichloride,(pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconiumdichloride,(tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconiumdichloride, or a mixture thereof.

In another embodiment, a first catalyst compound is combined with asupported activator in the slurry, and a second catalyst compound and anactivator are combined in the solution and thereafter the two are mixedin line. In another embodiment, the one activator is an alumoxane andthe other activator is a boron based activator.

In another embodiment the slurry comprises mineral oil, spray dried[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂, and the solution comprisesbis(n-propylcyclopentadienyl)zirconium dichloride.

In a one embodiment of this invention the slurry comprises supportedactivator and a catalyst compound and the solution comprises a catalystcompound different in some way from the catalyst compound in the slurry.For example, the slurry catalyst compound could be a compoundrepresented by the Formula I or II described above, while the solutioncatalyst compound could be a catalyst compound described by Formula III,IV, V, VI, or VII, or vice versa.

In another embodiment, if a bimodal polymer product were desired, onecould mix a first catalyst compound with an activator in the slurry,then on-line add a solution of a different catalyst compound that iscapable of being activated by the same activator. Since the two catalystcompounds are introduced into the feed line independently, it will beeasier to control the amount of the two species in the final bimodalproduct, assuming that each catalyst produces at least one species ofpolymer.

In another embodiment, a Group 15 metal containing compound and a bulkyligand metallocene catalyst compound are combined with supportedalumoxane in the process of this invention. Typically the two catalystcompounds are combined in the slurry with the supported alumoxane andthe solution will comprise a trim solution of one or the other of thetwo catalyst compounds.

In another embodiment, [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂, andbis(n-propyl cyclopentadienyl) zirconium dichloride are combined withsupported methyl alumoxane in the process of this invention. Typicallythe two catalyst compounds are combined in the slurry with the supportedalumoxane and the solution will comprise one or the other of the twocatalyst compounds. The solution is preferably used as a trim solutionto regulate the product formed in the reactor by varying the amount ofsolution combined with the slurry on-line, i.e. to trim the mix. In oneembodiment this catalyst combination is then used to polymerizeolefin(s), preferably ethylene, at a polymerization temperature of 80 to110° C. and in the presence of little or no comonomer(s) for examplehexene.

In another embodiment the slurry concentration is maintained at greaterthan 0 to 90 wt % solids, more preferably 1 to 50 wt %, more preferably5 to 40 wt %, even more preferably 10 to 30 wt %, based upon the weightof the slurry. In another preferred embodiment the activator is presenton the support at between about 0.5 to about 7 mmol/g, preferably about2 to about 6 mmol/g, more preferably between about 4 to about 5 mmol/g.In another preferred embodiment the total amount of catalyst compoundpresent on the support, preferably a supported activator, is about 1 toabout 40 μmol/g, preferably about 10 to about 38 μmol/g, more preferably30 to 36 μmol/g.

In one embodiment the final mole ratio (i.e. after combination of thesolution and the slurry) of the metal of the catalyst compounds and themetal of the activator is in the range of from about 1000:1 to about0.5:1 preferably from about 300:1 to about 1:1 more preferably fromabout 150:1 to about 1:1; for boranes, borates, aluminates, etc., theratio is preferably about 1:1 to about 10:1 and for alkyl aluminumcompounds (such as diethylaluminum chloride combined with water) theratio is preferably about 0.5:1 to about 10:1.

In one embodiment, the catalyst compound used in the slurry is notsoluble in the solvent used in the solution. By “not soluble” is meantthat the not more than 5 weight % of the material dissolves into thesolvent at 20° C. and less than 3 minutes of stirring, preferably notmore than 1 weight %, preferably not more than 0.1 weight %, preferablynot more than 0.01 weight %. In a preferred embodiment, the catalystcompound used in the slurry at least only sparingly soluble in anaromatic hydrocarbon. In a particularly preferred embodiment thecatalyst compound used in the slurry is not soluble in mineral oil,aromatic solvent or aliphatic hydrocarbon (pentane, heptane, etc.).

D. Delivery of the Catalyst Composition

In the process of the invention, the catalyst component slurry iscombined with and/or reacted with the catalyst component solution toform a catalyst composition in-line. The catalyst composition so formedis then is introduced into the polymerization reactor. Generally thecatalyst composition is introduced to the reactor utilizing a catalystfeed system which includes a catalyst component slurry holding vessel, acatalyst component solution holding vessel, and a slurry feeder.

Referring to FIG. 1, in one embodiment, the catalyst component slurry,preferably a mineral oil slurry including at least one support and atleast one activator, preferably at least one supported activator, andoptional catalyst compound(s) is placed in a vessel (A). In a preferredembodiment (A) is an agitated holding tank designed to keep the solidsconcentration homogenous. The catalyst component solution, prepared bymixing a solvent and at least one catalyst compound and/or activator, isplaced in a vessel (C). The catalyst component slurry is then combinedin-line with the catalyst component solution to form a final catalystcomposition. A nucleating agent, such as silica, alumina, fumed silicaor any other particulate matter (B) may be added to the slurry and/orthe solution in-line or in the vessels (A) or (C). Similarly, additionalactivators or catalyst compounds may be added in-line. The catalystcomponent slurry and solution are preferably mixed in-line at some point(E) for a period of time. For example, the solution and slurry may bemixed by utilizing a static mixer or an agitating vessel. The mixing ofthe catalyst component slurry and the catalyst component solution shouldbe long enough to allow the catalyst compound in the catalyst componentsolution to disperse in the catalyst component slurry such that thecatalyst component, originally in the solution, migrates to thesupported activator originally present in the slurry. The combinationthereby becomes a uniform dispersion of catalyst compounds on thesupported activator forming the catalyst composition of the invention.The length of time that the slurry and the solution are contacted istypically up to about 120 minutes, preferably about 1 to about 60minutes, more preferably about 5 to about 40 minutes, even morepreferably about 10 to about 30 minutes.

In another embodiment, an aluminum alkyl, an ethoxylated aluminum alkyl,an alumoxane, an anti-static agent or a borate activator, such as a C₁to C₁₅ alkyl aluminum (for example tri-isobutyl aluminum, trimethylaluminum or the like), a C₁ to C₁₅ ethoxylated alkyl aluminum or methylalumoxane, ethyl alumoxane, isobutylalumoxane, modified alumoxane or thelike are added to the mixture of the slurry and the solution in line.The alkyls, antistatic agents, borate activators and/or alumoxanes maybe added (F), directly to the combination of the solution and theslurry, or may be added via an additional alkane (such as isopentane,hexane, heptane, and or octane) carrier stream (G). Preferably, theadditional alkyls, antistatic agents, borate activators and/oralumoxanes are present at up to about 500 ppm, more preferably at about1 to about 300 ppm, more preferably at 10 to about 300 ppm, morepreferably at about 10 to about 100 ppm. Preferred carrier streamsinclude isopentane and or hexane. The alkane may be added (G) to themixture of the slurry and the solution, typically at a rate of about 0.5to about 60 lbs/hr (27 kg/hr). Likewise carrier gas, such as nitrogen,argon, ethane, propane and the like may be added in-line (H) to themixture of the slurry and the solution. Typically the carrier gas may beadded at the rate of about 1 to about 100 lb/hr (0.4 to 45 kg/hr),preferably about 1 to about 50 lb/hr (5 to 23 kg/hr), more preferablyabout 1 to about 25 lb/hr (0.4 to 11 kg/hr).

In another embodiment, a liquid carrier stream is introduced into thecombination of the solution and slurry that is moving in a downwarddirection. The mixture of the solution, the slurry and the liquidcarrier stream may pass through an optional mixer or length of tube formixing before being contacted with a gaseous carrier stream.

Similarly, hexene (or other alpha-olefin or diolefin) may be addedin-line (J) to the mixture of the slurry and the solution. Theslurry/solution mixture is then preferably passed through an injectiontube (O) to the reactor (Q). In some embodiments, the injection tube mayaerosolize the slurry/solution mixture. In a preferred embodiment theinjection tube has a diameter of about {fraction (1/16)} inch to about ½inch (0.16 cm to 1.27 cm), preferably about {fraction (3/16)} inch toabout ⅜ inch (0.5 cm to 0.9 cm), more preferably ¼ inch to about ⅜thsinch (0.6 cm to 0.9 cm).

In one embodiment cycle gas (also called re-cycle gas) is introducedinto the support tube (S), in another embodiment monomer gas, such asethylene gas, is introduced into the support tube. Nucleating agents(K), such as fumed silica, can be added directly in to the reactor.

In another embodiment a plenum may be used in this invention. A plenumis a device used to create a particle lean zone in a fluidized bedgas-phase reactor, as described in detail in U.S. Pat. No. 5,693,727which is incorporated herein by reference. A plenum may have one, two,or more injection nozzles.

In another embodiment when a metallocene catalyst or other similarcatalyst is used in the gas phase reactor, oxygen and or fluorobenzenecan be added to the reactor directly or to the recycle gas to affect thepolymerization rate. Thus, when a metallocene catalyst (which issensitive to oxygen or fluorobenzene) is used in combination withanother catalyst (that is not sensitive to oxygen) in a gas phasereactor, oxygen can be used to modify the metallocene polymerizationrate relative to the polymerization rate of the other catalyst. Anexample of such a catalyst combination is bis(n-propylcyclopentadienyl)zirconium dichloride and[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂, where Me is methyl orbis(indenyl)zirconium dichloride and [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂,where Me is methyl. For example if the oxygen concentration in thenitrogen feed is altered from 0.1 ppm to 0.5 ppm, significantly lesspolymer from the bisindenyl ZrCl₂ will be produced and the relativeamount of polymer produced from the [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHHfBz₂ isincreased. WO/09328 discloses the addition of water and or carbondioxide to gas phase polymerization reactors.

In another embodiment, referring still to FIG. 1, the slurry comprisingmineral oil, at least one catalyst compound, a support and an activatoris mixed in and/or introduced from (A). The catalyst component solutioncomprising a solvent, such as toluene, hexane, mineral oil ortetrahydrofuran, and a catalyst compound and/or an activator is mixed inand/or introduced from (C). Nucleating agent (B) and (K), such as fumedsilica, may be added on line at one or more positions and may be wet ordry. The slurry and the solution are combined and typically mixed at(E). Optional light alkyls (F), such as triisobutyl aluminum, analumoxane, modified methylalumoxane and/or trimethyl aluminum, may beadded in line directly to the combination or via an alkane, such asisopentane, feed (G). Nitrogen (H) and/or olefin, such as hexene, (J)may also be added in line. The combination may then be injected throughan injection tube (O) (such as a ⅛ inch (0.3 cm) tube) into a gas phasereactor (Q). The injection tube (O) may be supported inside a largersupport tube (S), such as a 1 inch (2.54 cm) tube. Oxygen can be addeddirectly to the reactor (Q) or to the recycle gas (P) to alter theactivity of one or more catalysts. (R) is flow (monomer, recycle gas,alkane) to the support tube (S).

In another embodiment, catalyst ball formation and or general nozzlefouling were reduced by first feeding isopentane carrier from the feedline (G) into the combination of the solution and the slurry, thereafterthe combination of the solution slurry and isopentane preferably movesin a vertical orientation with a downward flow into the reactor using anitrogen sweep (H) to disperse the isopentane/slurry mixture into thereactor.

The catalyst injection tube passes into the reactor through a compressedchevron packing and extends into the fluid bed a distance of about 0.1inch to 10 feet (0.25 cm to 3.1 m), preferably about 1 inch to 6 ft (2.5cm to 1.8 m), and more preferably about 2 inches to 5 feet (5 cm to 1.5m). Typically, the depth of insertion depends on the diameter of thereactor and typically extends in about {fraction (1/20)} to ½ of thereactor diameter, preferably about {fraction (1/10)}th to ½ and morepreferably about ⅕th to ⅓rd o diameter. The end of the tube may be cutperpendicular to the axis to create a nozzle cone or point with an angleranging from 0 to 90 degrees, preferably ranging from about 10 to 80degrees. The lip of the hole can be taken to a new knife-edge. The tubecan be positioned to reduce resin adhesion or coated with an antifoulingor antistatic compound. The tube can also be cut diagonally at an anglesimply from about 0 to 80 degrees off the axial line of the tube,preferably about 0 to 60 degrees. The opening of the tube can be thesame as the bore of the tube or expanded or diminished to create anozzle, with sufficient pressure drop and geometry to provide adispersed spray of a solution slurry and or powder into the reactor,preferably into the fluid bed.

The injection tube can optionally be supported inside a structure withinthe fluid bed to provide structural integrity. This support tube istypically a heavy walled pipe with an internal diameter of from about ¼inch to about 5 inches (0.64 cm to 12.7 cm), preferably about ½ inch toabout 3 inches (1.3 cm to 7.6 cm), and more preferably about ¾ inch toabout 2 inches (1.9 cm to 5 cm). The support tube preferably extendsthrough the reactor wall to approximately the length of the injectiontube, allowing the injection tube to end just inside the end of thesupport tube or to extend past it up to about 10 inches (25.4 cm).Preferably, the injection tube extends about 0.5 to 5 inches (1.8 cm to12.7 cm) beyond the end of the support tube and more preferably about 1to 3 inches (2.5 cm to 7.6 cm). The end of the support tube in thereactor may be cut flat and perpendicular to the axis of the tube orpreferably, may be tapered at an angle ranging from about 10 to 80degrees. The end of the support tube may be polished or coated with ananti-static or anti-fouling material.

A purge flow of fluid (R) (typically fresh monomer, ethylene, hexane,isopentane, recycle gas, and the like) is preferably introduced fromoutside the reactor down the support tube to aid in dispersion of thecatalyst composition allowing the production of resin granular particlesof good morphology with decreased agglomeration and an APS (averageparticle size) in the range of about 0.005 to 0.10 inches (0.01 cm to0.3 cm). The purge flow of fluid helps minimize fouling of the end ofthe catalyst injection tube and support tubes. The fluid introduced tothe support tube may comprise hydrogen; olefins or diolefins, includingbut not limited to C₂ to C₄₀ alpha olefins and C₂ to C₄₀ diolefins,ethylene, propylene, butene, hexene, octene, norbornene, pentene,hexadiene, pentadiene, isobutylene, octadiene, cyclopentadiene,comonomer being used in the polymerization reaction, hydrogen; alkanes,such C₁ to C₄₀ alkanes, including but not limited to isopetane, hexane,ethane, propane, butane, and the like; mineral oil, cycle gas with orwithout condensed liquids; or any combination thereof. Preferably thesupport tube flow is fresh ethylene or propylene that may be heated. Inaddition, an alkane, such as for instance isopentane or hexane, can beincluded in the flow at the level ranging from about 0.001 wt %. toabout 50% of the flow. The alkane can be dispersed in the flow and mayexist as dispersed liquid droplets or be vaporized at the exit of thesupport tube. The presence of liquid may reduce fouling at the exit.

The flow rate of fluid in the support tube ranges from about 5 to 10,000pph and is somewhat dependent upon the reactor size. The linear velocityof the fluid in the support tube ranges from about 10 to 500 ft/sec (11to 549 km/hr), preferably about 20 to 300 ft/sec (22 to 329 km/hr) andmore preferably about 30 to 200 ft/sec (33 to 219 km/hr).

Alternatively, the exit of the support tube may be fashioned as a nozzleat the end to form a jet or dispersion of gas to aid in the distributionof the catalyst composition. In one embodiment, the internal diameter ofthe support tube is reduced gradually by about 3 to 80% at the end,preferably about 5 to 50% in a taper to create a nozzle to accelerate toand or disperse the fluid flow. The insertion of the injection tube isnot impacted by the internal taper of the support tube.

In another embodiment of the invention the contact time of the slurryand the solution can be varied to adjust or control formation of theactive catalyst complex. The contact time of the slurry and the solutionis preferably in the range of from 1 minute to 120 minutes, preferablyin the range of from 2 minutes to 60 minutes, preferably 5 minutes to 45minutes, more preferably from about 10 minutes to about 30 minutes.

In another embodiment, the contact temperature of the slurry and thesolution is in the range of from 0° C. to about 80° C., preferably fromabout 0° C. to about 60° C., more preferably from about 10° C. to about50° C. and most preferably from about 20° C. to about 40° C.

In another embodiment, the invention provides introducing theimmobilized catalyst system in the presence of a mineral oil or asurface modifier or a combination thereof as described in PCTpublication WO 96/11960 and U.S. Ser. No. 09/113,261 filed Jul. 10,1998, which are herein fully incorporated by reference. In anotherembodiment a slurry or surface modifier, such as an aluminum stearate inmineral oil) is introduced (T) into the reactor with the combination ofthe slurry and the solution. In another embodiment the surface modifier,such as aluminum stearate, was added into the slurry vessel (A).

In another embodiment the one or all of the catalysts are combined withup to 6 weight % of a metal stearate, (preferably a aluminum stearate,more preferably aluminum distearate) or an anti-static agent based uponthe weight of the catalyst, any support and the stearate or anti-staticagent, preferably 2 to 3 weight %. In one embodiment, a solution orslurry of the metal stearate or anti-static agent is fed into thereactor. The stearate or anti-static agent may be combined with theslurry (A) or the solution (C) or may be co-fed (R) with the combinationof the slurry and the solution. In a preferred embodiment the catalystcompounds and or activators are combined with about 0.5 to about 4weight % of an antistat, such as a methoxylated amine, such as Witco'sKemamine AS-990 from ICI Specialties in Bloomington Del.

In another embodiment the catalyst system or the components thereof arecombined with benzil, xylitol, Irganox™ 565, sorbitol or the like andthen fed into the reactor. These agents may be combined with thecatalyst compounds and/or activators or may be fed into the reactor in asolution with or without the catalyst system or its components.Similarly these agents may be combined with the slurry (A) or thesolution (C) or may be co-fed (R) with the combination of the slurry andthe solution.

In another embodiment the process of this invention may further compriseadditional solutions and slurries. For example, in a preferredembodiment a slurry can be combined with two or more solutions havingthe same or different catalyst compounds and or activators. Likewise,the solution may be combined with two or more slurries each having thesame or different supports, and the same or different catalyst compoundsand or activators. Similarly the process of this invention may comprisetwo or more slurries combined with two or more solutions, preferablyin-line, where the slurries each comprise the same or different supportsand may comprise the same or different catalyst compounds and oractivators and the solutions comprise the same or different catalystcompounds and or activators. For example, the slurry may contain asupported activator and two different catalyst compounds, and twosolutions, each containing one of the catalysts in the slurry, are eachindependently combined, in-line, with the slurry.

E. Use of Catalyst Composition to Control Product Properties

The timing, temperature, concentrations, and sequence of the mixing ofthe solution, the slurry and any optional added materials (nucleatingagents, catalyst compounds, activators, etc) described above can be usedto alter product properties. The melt index, relative amount of polymerproduced by each catalyst, and other properties of the polymer producedmay also be changed by manipulating process parameters which includemanipulating hydrogen concentration in the polymerization system or by:

1) changing the amount of the first catalyst in the polymerizationsystem, and/or

2) changing the amount of the second catalyst in the polymerizationsystem, and/or

3) changing the hydrogen concentration in the polymerization process;and/or

4) changing the relative ratio of the catalyst in the polymerizationprocess (and optionally adjusting their individual feed rates tomaintain a steady or constant resin production rate); and/or

5) changing the amount of liquid and/or gas that is withdrawn and/orpurged from the process; and/or

6) changing the amount and/or composition of a recovered liquid and/orrecovered gas returned to the polymerization process, said recoveredliquid or recovered gas being recovered from polymer discharged from thepolymerization process; and/or

7) using a hydrogenation catalyst in the polymerization process; and/or

8) changing the polymerization temperature; and/or

9) changing the ethylene partial pressure in the polymerization process;and/or

10) changing the ethylene to comonomer ratio in the polymerizationprocess; and/or

11) changing the activator to transition metal ratio in the activationsequence; and/or

12) changing the relative feed rates of the slurry and/or solution;and/or

13) changing the mixing time, the temperature and or degree of mixing ofthe slurry and the solution in-line; and/or

14) adding different types of activator compounds to the polymerizationprocess; and/or

15) adding oxygen or fluorobenzene or other catalyst poison to thepolymerization process.

For example to alter the flow index and or melt index of a polymerproduced according to the invention using a slurry of supportedmethylalumoxane and [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂ and a solution ofbis(n-propylcyclopentadienyl)zirconium dichloride one can alter thetemperature of the reaction in the polymerization reactor, one can alterthe concentration of hydrogen in the reactor, or one can alter theconcentration of the bis(n-propylcyclopentadienyl)zirconium dichloridein the solution prior to contacting the solution with the slurry, or onecan alter the relative feed rate of the catalyst component solutionand/or the catalyst component slurry.

In a preferred embodiment, the flow index (I₂₁—measured according toASTM D-1238, Condition E, at 190° C.) of the polymer product is measuredat regular intervals and one of the above factors, preferablytemperature, catalyst compound feed rate, the ratio of the two or morecatalysts to each other, monomer partial pressure, oxygen concentration,and or hydrogen concentration, is altered to bring the flow index to thedesired level, if necessary. Preferably the samples for flow indexmeasurements are melt-homogenized by extruding in an extruder that isequipped with either a single screw, preferably with a mixing head, or atwin screw, to make either tape or strand(s). The tape and or strandsare typically cut into small pieces for flow property measurements.

In an embodiment, a polymer product property is measured in-line and inresponse the ratio of the catalysts being combined is altered. In oneembodiment, the molar ratio of the catalyst compound in the catalystcomponent slurry to the catalyst compound in the catalyst componentsolution, after the slurry and solution have been mixed to form thefinal catalyst composition, is 500:1 to 1:500, preferably 100:1 to1:100, more preferably 50:1 to 1:50 and most preferably 40:1 to 1:10. Inanother embodiment, the molar ratio of a Group 15 catalyst compound inthe slurry to a bulky ligand metallocene catalyst compound in thesolution, after the slurry and solution have been mixed to form thecatalyst composition, is 500:1, preferably 100:1, more preferably 50:1,more preferably 10:1 and even more preferably 5:1. Preferably, theproduct property measured is the polymer product's flow index, meltindex, density, MWD, comonomer content and combinations thereof. Inanother embodiment, when the ratio of the catalyst compounds is altered,the introduction rate of the catalyst composition to the reactor, orother process parameters, is altered to maintain a desired productionrate.

Likewise, the support architecture, the number of functional groups onthe support (such as —OH groups on silica) the activator loading and thepre-impregnated catalyst loading can also affect the product formed.

Similarly, altering the ethylene partial pressure can alter productproperties. For example in a system where the solution comprisedbis(n-propyl cyclopentadienyl)zirconium dichloride and the slurrycomprised [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ and supported methylalumoxane, increasing the ethylene partial pressure in the gas phasereactor from 220 to 240 psi (1.5-1.7 MPa) increased the Flow Index from100 to over 700 dg/min.

While not wishing to be bound by or limited to any theory, the inventorsbelieve, that the processes described herein immobilize the solutioncatalyst compound in and on a support, preferably a supported activator.The in-line immobilization techniques described herein preferably resultin a supported catalyst system that when introduced to the reactorprovides for better particle morphology, bulk density, and/or highercatalyst activities and without the need for additional equipment inorder to introduce catalyst compound solution into a reactor,particularly a gas phase or slurry phase reactor. It is known in the artthat typical support techniques for supporting, metallocene catalystcompounds results in lower overall productivity of the formed supportedcatalysts. In some instances the supporting process in fact renderscertain of these catalyst compounds useless in commercial polymerizationprocesses that especially prefer the utilization of supported catalysts.This is particularly true when comparing introducing an unsupportedcatalyst system into a gas phase process versus a conventional supportedcatalyst system. By conventional supported catalysts system it is meantthose supported catalyst systems that are formed by contacting a supportmaterial, an activator and a catalyst compound in various ways under avariety of conditions outside of a catalyst feeder apparatus. Examplesof conventional methods of supporting metallocene catalyst systems aredescribed in U.S. Pat. Nos. 4,701,432, 4,808,561, 4,912,075, 4,925,821,4,937,217, 5,008,228, 5,238,892, 5,240,894, 5,332,706, 5,346,925,5,422,325, 5,466,649, 5,466,766, 5,468,702, 5,529,965, 5,554,704,5,629,253, 5,639,835, 5,625,015, 5,643,847, 5,665,665, 5,698,487,5,714,424, 5,723,400, 5,723,402, 5,731,261, 5,759,940, 5,767,032,5,770,664, 5,846,895 and 5,939,348 and U.S. application Ser. Nos.271,598 filed Jul. 7, 1994 and 788,736 filed Jan. 23, 1997 and PCTpublications WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297, andEP-B1-0 685 494. It was also surprisingly discovered that catalystsystems not commercially supportable in a gas phase process inparticular were found to be useful when immobilized using the process ofthe invention.

VI. Polymerization Process

The catalyst systems prepared and the method of catalyst system additiondescribed above are suitable for use in any prepolymerization and/orpolymerization process over a wide range of temperatures and pressures.The temperatures may be in the range of from −60° C. to about 280° C.,preferably from 50° C. to about 200° C., and the pressures employed maybe in the range from 1 atmosphere to about 500 atmospheres or higher.

Polymerization processes include solution, gas phase, slurry phase and ahigh pressure process or a combination thereof. Particularly preferredis a gas phase or slurry phase polymerization of one or more olefins atleast one of which is ethylene or propylene.

In one embodiment, the process of this invention is directed toward asolution, high pressure, slurry or gas phase polymerization process ofone or more olefin monomers having from 2 to 30 carbon atoms, preferably2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. Theinvention is particularly well suited to the polymerization of two ormore olefin monomers of ethylene, propylene, butene-1,pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

Other monomers useful in the process of the invention includeethylenically unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins. Non-limiting monomers useful in the invention mayinclude norbornene, norbornadiene, isobutylene, isoprene,vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidenenorbornene, dicyclopentadiene and cyclopentene.

In the most preferred embodiment of the process of the invention, acopolymer of ethylene is produced, where with ethylene, a comonomerhaving at least one alpha-olefin having from 3 to 15 carbon atoms,preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8carbon atoms, is polymerized in a gas phase process.

In another embodiment of the process of the invention, ethylene orpropylene is polymerized with at least two different comonomers,optionally one of which may be a diene, to form a terpolymer.

In an embodiment, the mole ratio of comonomer to ethylene, C_(x)/C₂,where C_(x) is the amount of comonomer and C₂ is the amount of ethyleneis between about 0.001 to 0.200 and more preferably between about 0.002to 0.008.

In one embodiment, the invention is directed to a polymerizationprocess, particularly a gas phase or slurry phase process, forpolymerizing propylene alone or with one or more other monomersincluding ethylene, and/or other olefins having from 4 to 12 carbonatoms. Polypropylene polymers may be produced using the particularlybridged bulky ligand metallocene catalysts as described in U.S. Pat.Nos. 5,296,434 and 5,278,264, both of which are herein incorporated byreference.

Typically in a gas phase polymerization process a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer. (See for exampleU.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749,5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228, allof which are fully incorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 100 psig(690 kPa) to about 600 psig (4138 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in a gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C.

Other gas phase processes contemplated by the process of the inventioninclude series or multistage polymerization processes. Also gas phaseprocesses contemplated by the invention include those described in U.S.Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, and European publicationsEP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 and EP-B-634 421 all ofwhich are herein fully incorporated by reference.

In a preferred embodiment, the reactor utilized in the present inventionis capable of and the process of the invention is producing greater than500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), evenmore preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still morepreferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even morepreferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferablygreater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr(45,500 Kg/hr).

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers and oftenhydrogen along with catalyst are added. The suspension including diluentis intermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

A preferred polymerization technique of the invention is referred to asa particle form polymerization, or a slurry process where thetemperature is kept below the temperature at which the polymer goes intosolution. Such technique is well known in the art, and described in forinstance U.S. Pat. No. 3,248,179 which is fully incorporated herein byreference. Other slurry processes include those employing a loop reactorand those utilizing a plurality of stirred reactors in series, parallel,or combinations thereof. Non-limiting examples of slurry processesinclude continuous loop or stirred tank processes. Also, other examplesof slurry processes are described in U.S. Pat. Nos. 4,613,484 and5,986,021, which are herein fully incorporated by reference.

In an embodiment the reactor used in the slurry process of the inventionis capable of and the process of the invention is producing greater than2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr(4540 Kg/hr). In another embodiment the slurry reactor used in theprocess of the invention is producing greater than 15,000 lbs of polymerper hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

Examples of solution processes are described in U.S. Pat. Nos.4,271,060, 5,001,205, 5,236,998, 5,589,555 and 5,977,251 and PCT WO99/32525 and PCT WO 99/40130, which are fully incorporated herein byreference

A preferred process of the invention is where the process, preferably aslurry or gas phase process is operated in the presence of a bulkyligand metallocene catalyst system of the invention and in the absenceof or essentially free of any scavengers, such as triethylaluminum,trimethylalumium, tri-isobutylaluminum and tri-n-hexylaluminum anddiethyl aluminum chloride, dibutyl zinc and the like. This preferredprocess is described in PCT publication WO 96/08520 and U.S. Pat. Nos.5,712,352 and 5,763,543, which are herein fully incorporated byreference.

In one embodiment of the invention, olefin(s), preferably C₂ to C₃₀olefin(s) or alpha-olefin(s), preferably ethylene or propylene orcombinations thereof are prepolymerized in the presence of themetallocene catalyst systems of the invention described above prior tothe main polymerization. The prepolymerization can be carried outbatchwise or continuously in gas, solution or slurry phase including atelevated pressures. The prepolymerization can take place with any olefinmonomer or combination and/or in the presence of any molecular weightcontrolling agent such as hydrogen. For examples of prepolymerizationprocedures, see U.S. Pat. Nos. 4,748,221, 4,789,359, 4,923,833,4,921,825, 5,283,278 and 5,705,578 and European publication EP-B-0279863 and PCT Publication WO 97/44371 all of which are herein fullyincorporated by reference.

In one embodiment, toluene is not used in the preparation orpolymerization process of this invention.

VII. Polymer Products

The polymers produced by the process of the invention can be used in awide variety of products and end-use applications. The polymers producedby the process of the invention include linear low density polyethylene,elastomers, plastomers, high density polyethylenes, medium densitypolyethylenes, low density polyethylenes, multimodal or bimodal highmolecular weight polyethylenes, polypropylene and polypropylenecopolymers.

The polymers, typically ethylene based polymers, have a density in therange of from 0.86 g/cc to 0.97 g/cc, depending on the desired use. Forsome applications a density in the range of from 0.88 g/cc to 0.920 g/ccis preferred while in other applications, such as pipe, film and blowmolding, a density in the range of from 0.930 g/cc to 0.965 g/cc ispreferred. For low density polymers, such as for film applications, adensity of 0.910 g/cc to 0.940 g/cc is preferred. Density is measured inaccordance with ASTM-D1238.

The polymers produced by the process of the invention may have amolecular weight distribution, a ratio of weight average molecularweight to number average molecular weight (M_(w)/M_(n)), of greater than1.5 to about 70. In some embodiments the polymer produced has a narrowM_(w)/M_(n) of about 1.5 to 15, while in other embodiments the polymerproduced has an M_(w)/M_(n) of about 30 to 50. Also, the polymers of theinvention may have a narrow or broad composition distribution asmeasured by Composition Distribution Breadth Index (CDBI). Furtherdetails of determining the CDBI of a copolymer are known to thoseskilled in the art. See, for example, PCT Patent Application WO93/03093, published Feb. 18, 1993, which is fully incorporated herein byreference. In some embodiments the polymer produced may have a CDBI of80% or more or may have a CDBI of 50% or less.

The polymers of the invention in one embodiment have CDBI's generally inthe range of greater than 50% to 100%, preferably 99%, preferably in therange of 55% to 85%, and more preferably 60% to 80%, even morepreferably greater than 60%, still even more preferably greater than65%.

In another embodiment, polymers produced using this invention have aCDBI less than 50%, more preferably less than 40%, and most preferablyless than 30%.

The polymers of the present invention in one embodiment have a meltindex (MI) or (I₂) as measured by ASTM-D-1238-E in the range from 0.01dg/min to 1000 dg/min, more preferably from about 0.01 dg/min to about100 dg/min, even more preferably from about 0.01 dg/min to about 50dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.

The polymers of the invention in an embodiment have a melt index ratio(I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of from 10 to less than 25,more preferably from about 15 to less than 25.

The polymers of the invention in a preferred embodiment have a meltindex ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of frompreferably greater than 25, more preferably greater than 30, even morepreferably greater that 40, still even more preferably greater than 50and most preferably greater than 65. In an embodiment, the polymer ofthe invention may have a narrow molecular weight distribution and abroad composition distribution or vice-versa, and may be those polymersdescribed in U.S. Pat. No. 5,798,427 incorporated herein by reference.

In one embodiment the polymers produced by this invention have amultimodal molecular weight distribution (Mw/Mn) or, a typically,bimodal molecular weight distribution. In a preferred embodiment, thepolymer produced has a density of 0.93 to 0.96 g/cc, an MI (I₂) of0.03-0.10 g/10 min, an FI (I₂₁) of 4-12 g/10 min (I₂₁/I₂) of 80-180, anoverall Mw of 200,000 to 400,000, an overall Mn of 5,000-10,000 and anMw/Mn of 20-50. Preferably the low molecular weight fraction(˜500-˜50,000) has a density of 0.935-0.975 g/cc and the high molecularweight fraction (˜50,000-˜8,000,000) has a density of 0.910-0.950 g/cc.These polymers are particularly useful for film and pipe, especially,for PE-100 pipe applications. More preferably, this embodiment of thepolymer has the following molecular weight distribution (MWD)characteristics. The MWDs, as obtained from size exclusionchromatography (SEC), can be deconvoluted using the bimodal fittingprogram. The preferred split of the polymer, the ratio of Wt % of HMWfraction and the Wt % of LMW fraction, is 20-80 to 80-20, morepreferably 30-70 to 70-30, and even more preferably 40-60 to 60-40.Higher Wt % of HMW than LMW Wt % is preferred. The SEC curve can befurther analyzed to give percent of Wt %>1 MM, which is the weightpercent of the total MWD that has a molecular weight greater than 1million, and Wt %>100K, which is the weight percent of the total MWDthat is greater than 100,000 in molecular weight. The weight percentratio is simply Wt %>1 MM divided by Wt %>100K. 100,000 was used as anapproximate means of dividing the total MWD into a HMW (high molecularweight) and LMW (low molecular weight) region. This ratio gives a simplebut sensitive indication of the relative amount of the very highmolecular weight species in the HMW region of the MWD. The preferredembodiment of the polymer has the preferred range of weight percentration (WPR), higher than 10 but less than 30, preferably higher than 15but less than 25. The stability of blown bubble during film extrusion isfound to depend on this WPR as shown in the table below. A preferredcatalyst system to produce these polymers according to this inventioncomprises [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}HfBz₂ or[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}ZrBz₂ combined with bis(indenyl)zirconiumdichloride,(pentamethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconiumdichloride or(tetramethylcyclopentadienyl)(n-propylcyclopentadienyl)zirconiumdichloride, and supported methylalumoxane.

HMW HMW wt % Bubble Sample FI MI MFR Mw % Split Wt % > 1 MM Wt % > 100 KRatio Stability No. 1 8.32 0.051 167.3 605,500 53.5% 9.7% 41.8% 23% PoorNo. 2 7.45 0.06 124 584,000 50.1% 8.7% 41.7% 21% Good No. 3 7.99 0.047168.7 549,900 53.3% 8.7% 40.9% 21% Good No. 4 9.16 0.076 121.2 454,70058.3% 7.5% 42.1% 18% Good No. 5 8.11 0.094 86.7 471,800 53.7% 6.6% 43.3%15% Poor

A typical SEC curve of the embodiment of the polymer is shown in theFIG. 5. Two distinctive peaks of HMW and LMW fractions can be seen withthe deconvoluted curves.

LMW HMW Overall Mn: 3,231 91,514 8,076 Mw: 12,307 505,322 291,217 Mw/Mn:3.81 5.52 36.06 Wt %: 43.57% 56.43%

This multimodal or bimodal polymer is found to exhibit excellent bubblestability and good film extrusion characteristics. The polymerdemonstrated excellent draw-down characteristics and as thin as 0.35 milfilm was obtained. The film appearance rate was excellent with no speckof gels. The film dart impact strength was excellent suitable which issuitable for grocery sacks applications.

In another embodiment the polymer produced by this invention has abimodal molecular weight distribution (Mw/Mn). In a preferredembodiment, the polymer produced has a density of 0.93 to 0.97 g/cc, anMI (I₂) of 0.02-0.5 g/10 min, an FI (I₂₁) of 10-40 g/10 min, an MFR(I₂₁/I₂) of 50-300, an Mw of 100,000 to 500,000, an Mn of 8,000-20,000and an Mw/Mn of 10-40. These polymers are particularly useful for blowmolding applications. These bimodal polymers exhibited extraordinaryBent Strip ESCR (environmental stress crack resistance) performance,which far exceeds the performance of unimodal HDPE. Also, the blowmolded bottles trimmed easier and had opaque finish, which is preferredover translucent finish of unimodal HDPE.

In yet another embodiment, propylene based polymers are produced in theprocess of the invention. These polymers include atactic polypropylene,isotactic polypropylene, hemi-isotactic and syndiotactic polypropyleneor mixtures thereof produced by using two or more different catalysts inthe practice of this invention. Other propylene polymers includepropylene block or impact copolymers. Propylene polymers of these typesare well known in the art, see for example U.S. Pat. Nos. 4,794,096,3,248,455, 4,376,851, 5,036,034 and 5,459,117, all of which are hereinincorporated by reference.

The polymers of the invention may be blended and/or coextruded with anyother polymer. Non-limiting examples of other polymers include linearlow density polyethylenes produced via conventional Ziegler-Natta and/orbulky ligand metallocene catalysis, elastomers, plastomers, highpressure low density polyethylene, high density polyethylenes,polypropylenes and the like.

Polymers produced by the process of the invention and blends thereof areuseful in such forming operations as film, sheet, and fiber extrusionand co-extrusion as well as blow molding, injection molding and rotarymolding. Films include blown or cast films formed by coextrusion or bylamination useful as shrink film, cling film, stretch film, sealingfilms, oriented films, snack packaging, heavy duty bags, grocery sacks,baked and frozen food packaging, medical packaging, industrial liners,membranes, etc. in food-contact and non-food contact applications.Fibers include melt spinning, solution spinning and melt blown fiberoperations for use in woven or non-woven form to make filters, diaperfabrics, medical garments, geotextiles, etc. Extruded articles includemedical tubing, wire and cable coatings, pipe, geomembranes, and pondliners. Molded articles include single and multi-layered constructionsin the form of bottles, tanks, large hollow articles, rigid foodcontainers and toys, etc.

In another embodiment, the polymer of the invention is made into a pipeby methods known in the art. For pipe applications, the polymers of theinvention have a I₂₁ of from about 2 to about 10 dg/min and preferablyfrom about 2 to about 8 dg/min. In another embodiment, the pipe of theinvention satisfies ISO qualifications. In another embodiment, thepresent invention is used to make polyethylene pipe having a predictedS-4 T_(c) for 110 mm pipe of less than −5° C., preferably of less than−15° C. and more preferably less than −40° C. (ISO DIS 13477/ASTMF1589).

In another embodiment, the polymer has an extrusion rate of greater thanabout 17 lbs/hour/inch of die circumference and preferably greater thanabout 20 lbs/hour/inch of die circumference and more preferably greaterthan about 22 lbs/hour/inch of die circumference

The polyolefins of the invention can be made into films, molded articles(including pipes), sheets, wire and cable coating and the like. Thefilms may be formed by any of the conventional techniques known in theart including extrusion, co-extrusion, lamination, blowing and casting.The film may be obtained by the flat film or tubular process which maybe followed by orientation in a uniaxial direction or in two mutuallyperpendicular directions in the plane of the film to the same ordifferent extents. Orientation may be to the same extent in bothdirections or may be to different extents. Particularly preferredmethods to form the polymers into films include extrusion or coextrusionon a blown or cast film line.

In another embodiment, the polymer of the invention is made into a filmby methods known in the art. For film application, the polymers of theinvention have a I₂₁ of from about 2 to about 50 dg/min, preferably fromabout 2 to about 30 dg/min, even more preferably from about 2 to about20 dg/min, still more preferably about 5 to about 15 dg/min and yet morepreferably from about 5 to about 10 dg/min.

The objects produced (such as films, pipes, etc) may further containadditives such as slip, antiblock, antioxidants, pigments, fillers,antifog, UV stabilizers, antistats, polymer processing aids,neutralizers, lubricants, surfactants, pigments, dyes and nucleatingagents. Preferred additives include silicon dioxide, synthetic silica,titanium dioxide, polydimethylsiloxane, calcium carbonate, metalstearates, calcium stearate, zinc stearate, talc, BaSO₄, diatomaceousearth, wax, carbon black, flame retarding additives, low molecularweight resins, hydrocarbon resins, glass beads and the like. Theadditives may be present in the typically effective amounts well knownin the art, such as 0.001 weight % to 10 weight %.

In another embodiment, the polymer of the invention is made into amolded article by methods known in the art, for example, by blow moldingand injection-stretch molding. For molded applications, the polymers ofthe invention have a I₂₁ of from about 20 dg/min to about 50 dg/min andpreferably from about 35 dg/min to about 45 dg/min.

Further, while not wishing to be bound by any theory, it is believedthat the polymers produced by this invention have the unique advantageof the two polymer products being so intimately blended that there is aneven distribution of the two polymers across the polymer particles asthey exit the reactor. The unprocessed, untreated granular polymer isreferred to as neat polymer. The neat polymer is then separated intofractions by standard sieve sizes according to ASTM D 1921 particle size(sieve analysis) of Plastic Materials, Method A or PEG Method 507.

Sieve size Fraction Collected Fraction Name 10 mesh >2000 μm Fraction 118 mesh 2000-1000 μm Fraction 2 35 mesh <1000-500 μm Fraction 3 60 mesh<500-250 μm Fraction 4 120 mesh <250-125 μm Fraction 5 200 mesh/Pan <125μm Fraction 6 Overall Fraction 6

The individual fractions (Fraction 2, 3, 4, 5) are then tested forphysical properties. Melt index is measured according to ASTM 1238,condition E, 190° C.

A unique attribute of the polymer produced herein is that the meltindices of the different fractions do not vary significantly. In apreferred embodiment the melt indices of Fractions 3, 4 and 5 do notvary by more than 40% relative, preferably by not more than 30%relative, preferably by not more than 10% relative, preferably by notmore than 8% relative, preferably by not more that 6% relative,preferably by not more than 4% relative. Relative means relative to themean of the values for Fractions 3, 4 and 5.

In another embodiment, fractions 2, 3, 4 and 5 comprise more than 90% ofthe total weight of the resin sample; preferably fractions 2, 3 and 4comprise more than 90% of the total weight of the resin sample.

Another desirable attribute of the polymer produced herein is that theMw/Mn of the different fractions do not vary significantly. In apreferred embodiment the Mw/Mn of Fractions 1, 4, 5 and 6 do not vary bymore than 20% relative, preferably by not more than 10% relative,preferably by not more than 8% relative, preferably by not more than 6%relative, preferably by not more that 4% relative, preferably by notmore than 2% relative. In a preferred embodiment the Mw/Mn of Fractions1, 4 and 6 do not vary by more than 20% relative, preferably by not morethan 10% relative, preferably by not more than 8% relative, preferablyby not more than 6% relative, preferably by not more that 4% relative,preferably by not more than 2% relative. Relative means relative to themean of the values for Fractions 1, 4 and 6. In another preferredembodiment the Mw/Mn of Fractions 2, 3, 4 and 5 do not vary by more than20% relative, preferably by not more than 10% relative, preferably bynot more than 8% relative, preferably by not more than 6% relative,preferably by not more that 4% relative, preferably by not more than 2%relative. Relative means relative to the mean of the values forFractions 2, 3, 4 and 5. In a another preferred embodiment the Mw/Mn ofFractions 3, 4 and 5 do not vary by more than 20% relative, preferablyby not more than 10% relative, preferably by not more than 8% relative,preferably by not more than 6% relative, preferably by not more that 4%relative, preferably by not more than 2% relative. Relative meansrelative to the mean of the values for Fractions 3, 4 and 5. Mn and Mware measured by gel permeation chromatography on a waters 150° C. GPCinstrument equipped with differential refraction index detectors. TheGPC columns are calibrated by running a series of narrow polystyrenestandards and the molecular weights are calculated using broadpolyethylene standards National Bureau of Standards 1496 for the polymerin question.

In another preferred embodiment the polymer produced according to thisinvention comprises 10-90 weight % of low molecular weight polymer (lowis 50,000 or less preferably 40,000 or less), preferably 20 to 80 weight%, more preferably 40-60 weight %, based upon the weight of the polymer.

In one embodiment the fractions have the following characteristics.

Sieve Fraction Fraction size Collected Weight % I21 I5 I2 Name  10 >2000μm 0.5 Fraction 1 mesh  18 2000-1000 μm 1.02 23.9 0.75 0.14 Fraction 2mesh  35 <1000-500 μm 15.11 37.6 1.18 0.22 Fraction 3 mesh  60 <500-250μm 44.05 41.0 1.28 0.20 Fraction 4 mesh 120 <250-125 μm 33.62 40.8 .930.18 Fraction 5 mesh 200 <125 μm 5.70 Fraction 6 mesh/ Pan Overall 100.041.6 1.18 0.23 Fraction 6

In another embodiment the polyolefin produced is found to have at leasttwo species of molecular weights present at greater than 20 weight %based upon the weight of the polymer.

In another embodiment of this invention the polymer produced is bi- ormulti-modal (on the SEC graph). By bi- or multi-modal is meant that theSEC graph of the polymer has two or more positive slopes, two or morenegative slopes, and three or more inflection points (an inflectionpoint is that point where the second derivative of the curve becomesnegative) OR the graph has at least has one positive slope, one negativeslope, one inflection point and a change in the positive and or negativeslope greater than 20% of the slope before the change. In anotherembodiment the SEC graph has one positive slope, one negative slope, oneinflection point and an Mw/Mn of 10 or more, preferably 15 or more, morepreferably 20 or more. The SEC graph is generated by gel permeationchromatography on a waters 150° C. GPC instrument equipped withdifferential refraction index detectors. The columns are calibrated byrunning a series of narrow polystyrene standards and the molecularweights were calculated using Mark Houwink coefficients for the polymerin question.

The films produced using the polymers of this invention have extremelygood appearance properties. The films have a low gel content and/or havegood haze and gloss. In a preferred embodiment the 1 mil film (1.0mil=0.25 μm) has a 45° gloss of 7 or more, preferably 8 or more asmeasured by ASTM D 2475. In a preferred embodiment the 1 mil film (1.0mil=25 μm) has a haze of 75 of less, preferably 70 or less as measuredby ASTM D 1003, condition A.

In order to provide a better understanding of the present inventionincluding representative advantages thereof, the following examples areoffered.

EXAMPLES

Mn and Mw were measured by gel permeation chromatography on a waters150° C. GPC instrument equipped with differential refraction indexdetectors. The GPC columns were calibrated by running a series ofmolecular weight standards and the molecular weights were calculatedusing Mark Houwink coefficients for the polymer in question.

Density was measured according to ASTM D 1505.

Melt Index (MI) and Flow Index (FI) I₂ and I₂₁ were measured accordingto ASTM D-1238, Condition E, at 190° C.

Melt Index Ratio (MIR) is the ratio of I₂₁ over I₂ as determined by ASTMD-1238.

Weight % comonomer was measured by proton NMR.

MWD=M_(w)/M_(n)

Dart Impact was measured according to ASTM D 1709.

MD and TD Elmendorf Tear were measured according to ASTM D 1922.

MD and TD 1% Secant modulus were measured according to ASTM D 882.

MD and TD tensile strength and ultimate tensile strength were measuredaccording to ASTM D 882.

MD and TD elongation and ultimate elongation were measured according toASTM D 412.

MD and TD Modulus were measured according to ASTM 882-91

Haze was measured according to ASTM 1003-95, Condition A.

45° gloss was measured according to ASTM D 2457.

BUR is blow up ratio.

“PPH” is pounds per hour. “mPPH” is millipounds per hour. “ppmw” isparts per million by weight.

Example 1 Preparation of SMAO Supported Activator

For a 1 Kg batch, 1158.43 grams of 30 wt % MAO in toluene (7.3 wt % Al)available from Albemarle Corporation, Baton Rouge, La., and 2400 gramsof extra toluene are charged into an 8 liter mix tank equipped withribbon helical agitator. 984 grams of Davison 955-600 silica is added toMAO in toluene solution at ambient temperature. A 10° C. exotherm occursfrom reaction of the MAO with the hydroxyl groups. The slurry mixes for30 minutes at ambient temperature. Drying then occurs by heating the mixtank jacket to about 70° C. and reducing pressure to 0.00 mm/hg. As theslurry thickens the agitator rpm is reduced to minimum rotation, about40-60 RPM. Then the rotation is slowly increased (to about 600 RPM) andthe temperature is raised to 95° C. as the slurry turns to a dry powder.A nitrogen sweep (about 0.5 cc/min per gram of silica charged) can beused during the end of the drying step to help remove toluene from thesilica pores. The material is typically held at 95° C. until tolueneremoval stops, and material temperature lines out near jackettemperature. The material temperature does not change for at least 30minutes before the supported methylalumoxane (SMAO) is considered dry.Residual toluene is reduced to less than 2 wt % on the solids.

Example 2 Solution Catalyst Compound Activated with Slurry ComprisingSupported Activator in Fluidized Gas-Phase Reactor with Shorter ContactTime

Polymerization performance of in-line supported bis(n-propylcyclopentadienyl)zirconium dichloride (P-MCN) was evaluated in a 8 inch(20.3 cm) fluidized bed pilot plant reactor. The catalyst feedconfiguration is shown schematically in FIG. 2. P-MCN (1.7 umol/ml inhexane) was introduced in line at 0.65 g/hr. 0.5 weight % of TiBA inisopentane (200-250 cc/hr of isopentane carrier and 75-90 cc/hr of 0.5wt % TiBA) was introduced in line. Thereafter a slurry comprising Kaydolmineral oil and 16 weight % of SMAO produced in Example 1 (4.5 mmol/gsolids) was introduced in line and allowed to mix with the solution ofP-MCN and TiBA for 25-35 minutes. Following the mixer, the catalyst wasinjected using a standard ⅛ inch (0.32 cm) injection tube with 1.05 pphof N₂ blowback.

The catalyst was evaluated at LLDPE conditions, 75 C, 350 psig (2.4 MPa)total pressure, 120 psi (0.8 MPa) ethylene, 0.017 hexene-1 comonomer toethylene ratio. No hydrogen was fed to the reactor since this catalystmakes sufficient hydrogen to produce 2-5 dg/min melt index polymer underthe conditions employed. The superficial gas velocity (SGV) wasmaintained at 1.54 ft/s (0.47 m/s) and the steady state bed weight at 27lbs (12.3 kg). The reactor was operated continuously, i.e. forapproximately 13 hours per day, generally holding bed weight constant toyield a bed level near the top of the straight section. Where possible,the reactor was left closed overnight with the bed being fluidized in anitrogen atmosphere. TiBA (triisobutyl aluminum) in isopentane was fedas a scavenger at approximately 75 ppm in the bed to give catalystproductivity that is commercially relevant.

The product had a 6.1 dg/min (I2), 17.6 MFR and 0.93 g/cc density. Theresin average particle size was 0.022 inches (0.056 cm) with 2.4 wt %fines (<120 mesh). The settled bulk density was 27.4 lb/cu-ft. Aresidual zirconium of 0.66 ppm, aluminum of 33 ppm and silica of 75 ppmwas measured by ICP (Inductively Coupled Plasma spectroscopy).

Example 3 Solution Catalyst Compound Activated with Slurry ComprisingSupported Activator in Fluidized Gas-Phase Reactor with Longer ContactTime

Polymerization performance of in-line supported bis(n-propylcyclopentadienyl)zirconium dichloride (P-MCN) was evaluated in a 8 inch(20.3 cm) fluidized bed pilot plant reactor. The catalyst feedconfiguration is shown schematically in FIG. 3. P-MCN, fed at 0.56 g/hrwith 65-100 cc/hr of 0.5 wt % TIBA in isopentane upstream, was contactedwith 16 wt % SMAO (as produced in Example 1) in Kaydol mineral oilupstream of the 150 ml mixer. The solution and the slurry were allowedto mix for 90 to 130 minutes. 200-250 cc/hr of isopentane carrier wasused to sweep the catalyst exiting the mixer to the reactor. Followingthe mixer, catalyst was injected using a standard ⅛ inch (0.32 cm)injection tube with 1.1 pph N₂ blowback.

Catalyst was evaluated at LLDPE conditions, 75° C., 350 psig (2.4 MPa)total pressure, 120 psi (0.8 MPa) ethylene, 0.017 hexene-1 comonomer toethylene ratio. No hydrogen was fed to the reactor since this catalystmakes sufficient hydrogen to produce 2-5 dg/min melt index polymer underthe conditions employed. The superficial gas velocity (SGV) wasmaintained at 1.38 ft/s (0.42 m/s) and the steady state bed weight at30.5 lbs (13.6 kg). The reactor was operated continuously for ˜13 hoursper day, generally holding bed weight constant to yield a bed level nearthe top of the straight section. Where possible, the reactor was leftclosed overnight with the bed being fluidized in a nitrogen atmosphere.TIBA(triisobutyl alumium) in isopentane was fed as a scavenger at ˜75ppm in the bed to give catalyst productivity that is commerciallyrelevant.

The product had a 5.3 dg/min (I₂), 18.9 MFR and 0.928 g/cc density. Theresin average particle size was 0.021 inches (0.053 cm) with 2.8 wt %fines (<120 mesh). The settled bulk density was 26.0 lb/cu-ft. Aresidual zirconium of 0.55 ppm, aluminum of 35 ppm and silica of 78 ppmwas measured by ICP.

The data for Examples 2 and 3 are summarized in Table 1.

TABLE 1 8 INCH (20.3 CM) FLUIDIZED BED DATA SUMMARY Reaction ConditionsExample 2 Example 3 Production Rate 7.7 (3.5) 7.1 (3.2) (lb/hr)(kg/hr)@Steady State Fluidized Bulk 12-13.9 (192-223) 16-18.5 (256-296) Density(lb/ft³)(kg/m³) Seed Bed Quantity 11 (5) 22 (10) (lb)(kg) Bed Turnovers2.2 1.6 at Shutdown Theoretical wt % 0.11 0.19 seed bed at shutdownCatalyst Feed Parameters Cat Feed Rate (g/hr) 0.65 0.56 at SS, dry basisCatalyst Carriers Upstream of Mixer Isopentane (cc/hr) 200-250 na 0.5 wt% TIBA in 45-90 65-100 iC₅(cc/hr) Catalyst Carriers Downstream of MixerIsopentane (cc/hr) n/a 200-250 N₂ (lb/hr)(kg/hr) 1.05 (0.5) 1.1 (0.5)Resin Properties: Melt Index 6.1 5.3 I₂ dg/min MFR (I₂₁/I₂) 17.6 18.9Density (g/ml) 0.93 0.928 Bulk Density 27.4 (439) 26 (416)(lb/ft3)(kg/m³) Average Particle 0.022 (0.06) 0.021 (0.05) Size (in)(cm)Fines <120 mesh 2.4 2.8 (wt %) Quantity (lb) 69 (31.3) 51 (23.1) Net(kg) Zr Residue 0.66 0.55 (ppmw by ICP) Al Residue 33 35 (ppmw by ICP)Si Residue 75 78 (ppmw by ICP)

Example 4 Solution Catalyst Compound Activated with Slurry ComprisingSupported Activator in Fluidized Gas-Phase Reactor

Polymerization performance of in-line supported bis(n-propylcyclopentadienyl)zirconium dichloride (P-MCN) was evaluated in a 14 inch(35.6 cm) fluidized bed pilot plant reactor. The catalyst feedconfiguration used for in-line activation of P-MCN with SMAO is shown inFIG. 4. Catalyst solution, fed at 10 cc/hr, was contacted with 1.0 pphisopentane carrier and 10 cc/hr of 15 wt % SMAO (as produced inExample 1) in Kaydol mineral oil upstream of the 100 ml agitated mixer.Following the mixer, catalyst was injected using a standard ⅛ inch (0.3cm) injection tube with 2.0 pph N₂ blowback.

The catalyst system was evaluated at LLDPE conditions, 85° C., 350 psig(2.4 MPa) total pressure, 200 psi (1.4 MPa) ethylene, 0.0185 hexene-1comonomer to ethylene mole ratio (C₆/C₂). A concentration of 200 ppmhydrogen was maintained in the reactor. The superficial gas velocity(SGV) was maintained at 2.0 ft/s (0.6 m/s) and the steady state bedweight at 110 lbs (50 kg). The reactor production rate was at 31 pph.

The catalyst feed configuration used for in-line activation of P-MCNwith SMAO activator is shown in FIG. 4. Following the mixer, catalystwas injected using a standard ⅛ inch (0.3 cm) injection tube with 2.0pph N₂ blowback. Catalyst, fed at 10 cc/hr, was contacted with 1.0 pphisopentane carrier and 10 cc/hr of 15 wt % SMAO (as produced inexample 1) in Kaydol mineral oil upstream of the 100 ml agitated mixer.

The product had a 5.89 dg/min (I2), 16.6 MFR and 0.926 g/cc density. Theresin average particle size was 0.033 inches (0.084 cm) with 0.56 wt %fines (<120 mesh). The settled bulk density was 17.1 lb/cu-ft. Aresidual zirconium of 0.28 ppm and aluminum of 35 ppm was measured byX-ray fluorescence.

Example 5 Solution Bis-Indenyl Catalyst Compound Activated with SlurryComprising Supported Activator in Fluidized Gas-Phase Reactor

Polymerization performance of supported bis-indenyl zirconium dichloridesolution catalyst (bis-indenyl) was evaluated in a 14 inch (35.6 cm)fluidized bed pilot plant reactor. The catalyst feed configuration usedfor in-line activation of solution bis-indenyl metallocene catalystcompound with SMAO (from Example 1) is shown in FIG. 4. Catalyst, fed at15 cc/hr, was contacted with 0.5 pph isopentane carrier and 15 cc/hr of15 wt % SMAO in Kaydol mineral oil upstream of the 100 ml agitatedmixer. Following the mixer, catalyst was injected using a standard ⅛inch (0.32 cm) injection tube with 1.5 pph isopentane carrier and 4.0pph N₂ blowback.

The catalyst system was evaluated at LLDPE conditions, 85° C., 350 psig(2.4 MPa) total pressure, 200 psi (1.4 MPa) ethylene, 0.016 hexene-1comonomer to ethylene ratio (C₆/C₂). A concentration of 195 ppm hydrogenwas maintained in the reactor. The superficial gas velocity (SGV) wasmaintained at 2.0 ft/s (0.6 m/s) and the bed weight at 110 lbs (50 kg).The reactor production rate was 38 pph.

The product had a 8.4 dg/min (I2), 16.5 MFR and 0.9273 g/cc density. Theresin average particle size was 0.0357 inches (0.091 cm) with 0.44 wt %fines (<120 mesh). The settled bulk density was 18.4 lb/cu-ft. Aresidual zirconium of <0.10 ppm and aluminum of 27 ppm was measured byX-ray fluorescence.

Example 6 Solution P-MCN Catalyst Compound Activated with SlurryComprising SMAO and Second Catalyst Compound in Fluidized Gas-PhaseReactor

Polymerization performance of a solution comprisingbis(n-propylcyclopentadienyl)zirconium dichloride catalyst compound anda slurry comprising SMAO and [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ wasevaluated in a 14 inch (35.6 cm) fluidized bed pilot plant reactor. Thecatalyst feed configuration used for in-line activation of the solutionused the bis(n-propylcyclopentadienyl)zirconium dichloride at 0.5 weight%, and a slurry comprising 17.3 weight % SMAO (from Example 1) inKaydol. (The SMAO contained 4.5 mmol Al per gram of solid). The[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ added to the slurry off-line to make a150:1 molar ratio of Al:Zr. The remaining portion of the slurry wasKaydol mineral oil. Catalyst, fed at 4 cc/hr, was contacted with 75cc/hr of the SMAO/[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂ mixture in Kaydolmineral oil upstream of the series of two ten inch (25.4 cm) long ¼ inch(0.64 cm) diameter Kinecs static mixers (by Chemineer). The contact timebetween the solution and the slurry was approximately 5 minutes.Following the mixer, catalyst was injected using a standard ⅛ inch (0.32cm) injection tube with 3 pph isopentane carrier and 5 pph N₂ carrier.

The catalyst system was evaluated at the following conditions, 105° C.,350 psig (2.4 MPa) total pressure, 220 psi (1.5 MPa) ethylene, and0.0035 hexene-1 to ethylene molar ratio. A concentration of 1800 ppmhydrogen was maintained in the reactor. The superficial gas velocity(SGV) was maintained at 2.0 ft/s (0.6 m/s) and the bed weight at 75 lbs(34 kg). The reactor production rate was 21 pph.

The product had a 0.051 dg/min (I₂), 7.74 dg/min flow index, 151 MFR and0.9502 g/cc density. The resin average particle size was 0.016 inches(0.04 cm) with 1.25 wt % fines (<120 mesh). The settled bulk density was23.9 lb/cu-ft. A residual zirconium of <3.25 ppm and aluminum of 109 ppmwas measured by X-ray fluorescence.

The data of examples 4, 5 and 6 are summarized in Table 2.

TABLE 2 14 INCH (35.6 CM) FLUIDIZED BED DATA SUMMARY Example 4 Example 5Example 6 Fluidized Bulk 11.0 (176) 13.0 (208) 15.4 (247) Density(lb/ft³)(kg/m³) Bed Turnovers 10.3 8.7 12 at shutdown Resin PropertiesMelt Index 5.89 8.4 0.051 (I₂ (dg/min) Flow Index 97.65 138.7 7.74(I₂₁)(dg/min) MFR (I₂₁/I₂) 16.6 16.5 151 Density (g/cc) 0.926 0.92730.9502 Bulk Density 17.1 (274) 18.4 (295) 23.9 (383) (lb/ft³)(kg/m³)Average Particle 0.033 (0.08) 0.0357 (0.090) 0.016 (0.04) Size (in)(cm)Fines < 120 0.56 0.44 1.25 mesh (wt %) Zr residue 0.28 <0.10 3.25 (ppmby X-ray) Al residue 34.7 27 109 (ppm by X-ray)

Example 7

Several product samples made from polymerization with a slurrycomprising SMAO and [(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NHZrBz₂, and solutionbis(n-propylcyclopentadienyl)zirconium dichloride (P-MCN) catalyst wereevaluated for film applications. This bimodal HMW HDPE granular polymerwas compounded on a 2.5 inch, 24:1 L/D single screw, equipped withdouble mixing head, at 210° C., after tumble mixed with a stabilizerpackage comprising 1,000 ppm of Irganox 1076, 1,500 ppm of Irgafos 168,and 1,500 ppm of Calcium Stearate. Two pelleted samples showed 8.4 and9.9 FI, respectively, and 155 and 140 MFR. The density was 0.9524 and0.9490, respectively. The pelleted polymer was film extruded on anAlpine film line equipped with a 50 mm, 18:1 L/D single screw, a 100 mmdie with 1 mm die gap. The die temperature was set at 210° C. The outputwas maintained at about 100 lb/hr, the blow-up ratio of the bubble wasset at 4.0, and the frost line height was 36 inches. As shown in thetable below, the bimodal polymer exhibited excellent bubble stabilityand film extrusion characteristics. The film dart impact strength wasover 200 g and over 300 g, respectively for 1.0 mil and 0.5 mil gauge.The film samples also exhibited excellent tensile strength and modulus.

Sample No. Escorene HD 7755 A B Rxn Temp (° C.) 105 105 Rx pressure 350350 C2 PP 220 220 H2/C2 (molar) 0.003 0.003 H2 ppm 1800 1800 ComonomerC6 C6 Comonomer/C2 (molar) 0.004 0.0044 MI(I2) 0.068 0.055 0.071 MI(I5)0.341 FI(I21) 10 8.37 9.93 MFR (I21/I2) 146.6 155 140 Density (g/cc)0.9518 0.9524 0.9490 Ouput Rate (lb/hr) 100 101 104 Head pressure (psi)7,230 7,350 7,600 Motor Load (amp) 58 58.5 59.8 BUR 4 4 4 FLH (inch) 3636 36 Melt fracture no no no no no no FAR 40 40 40 40 40 40 BubbleStability Good fair Good Good Good Good Take-up speed (fpm) 92 182 92184 92 184 Film gauge (mil) 1 0.5 1 0.5 1 0.5 Dart Impact strength (g)250 330 200 340 230 340 Tensile strength (psi) MD 10,000 11,000 8,50011,820 8,600 12,800 TD 7,500 7,500 6,300 8,440 10,000 8,900 Elongation(%) MD 490 380 400 325 530 300 TD 570 390 630 370 430 380 Elmendorf Tear(g/mil) MD 22 12 22 11 21 12 TD 186 36 360 42 180 26 Modulus (psi) MD130,400 129,400 116,000 167,200 111,000 114,000 TD 160,200 163,000146,900 164,000 127,000 136,000

ESCORENE HD7755 is a polyethylene polymer available from ExxonMobilChemical Company in Mt. Belvue, Tex., having an I₂₁ of 7.5, and MIR of125, an Mw of 180,000, a density of 0.95 g/cc, produced using a dualreactor system.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For this reason, then, reference shouldbe made solely to the appended claims for purposes of determining thetrue scope of the present invention. It is also contemplated that thecombination of the slurry and the solution immobilization technique ofthe invention can be used to essentially form, for example, ametallocene catalyst compound that is combined with an activator and fedto a polymerization reactor.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures. As isapparent form the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly it is not intended thatthe invention be limited thereby.

We claim:
 1. A process to produce a multimodal polyolefin in a singlereactor comprising: a) continuously combining a catalyst componentslurry with a catalyst component solution to form a catalystcomposition; b) combining the catalyst composition with one or moreolefin(s) in a polymerization reactor to form a multimodal polyolefin;c) measuring a sample of the multimodal polyolefin to obtain an initialmultimodal polyolefin property; d) changing the amount of catalystcomponent solution combined in (a) relative to the amount of catalystcomponent slurry to obtain a second product property; and e) isolatingthe multimodal polyolefin product; wherein the catalyst component slurrycomprises one or more catalyst compounds, one or more activators and oneor more support materials; and the catalyst component solution comprisesone or more catalyst compounds, wherein the catalyst compounds may bethe same or different.
 2. The process of claim 1, wherein the catalystcomponent slurry comprises a first catalyst compound and the catalystcomponent solution comprises a second catalyst compound.
 3. The processof claim 2, wherein the first catalyst compound is a Group 15 containingmetal compound and where in the second catalyst compound is a bulkyligand metallocene compound.
 4. The process of claim 2, wherein themolar ratio of the first catalyst compound to the second catalystcompound in the catalyst composition is between about 500:1 to about1:500.
 5. The process of claim 1, wherein the polyolefin property isselected from the group consisting of flow index (I₂₁), melt index (I₂),density, MWD (M_(w)/M_(n)), comonomer content, and combinations thereof.6. The process of claim 1, wherein polyolefin property is flow index(I₂₁).
 7. The process of claim 1, wherein the reactor is a gas phasefluidized bed reactor.
 8. The process of claim 7, wherein the reactortemperature is from 60 to 115° C.
 9. The process of claim 1, wherein thecatalyst composition is passed through an injection tube extending intothe reactor a distance of 0.25 cm to 3.1 m.
 10. The process of claim 1,wherein the catalyst composition is passed through an injection tubeextending into the reactor a distance of 5 cm to 1.5 m.
 11. The processof claim 9 or 10, wherein a carrier stream comprising an alkane iscontacted with the catalyst composition prior to passing through theinjection tube.
 12. The process of claim 11, wherein the carrier streamfurther comprises a carrier gas.
 13. The process of claim 1, wherein thecatalyst component slurry comprises mineral oil.
 14. The process ofclaim 1, wherein the polyolefin product is a multimodal or bimodalpolyethylene comprising a high molecular weight fraction and a lowmolecular weigh fraction; the polymer product having a density of from0.930 g/cc to 0.965 g/cc and a Mw/Mn of from 20 to
 50. 15. The processof claim 1, wherein the polyolefin product is a multimodal or bimodalpolyethylene comprising a high molecular weight fraction and a lowmolecular weigh fraction; and wherein the weight percent ratio is higherthan 10 and less than
 30. 16. The process of claim 1, wherein thepolyolefin product is a multimodal or bimodal polyethylene comprising ahigh molecular weight fraction and a low molecular weigh fraction; andwherein the weight percent ratio is higher than 15 and less than
 25. 17.The process of claim 1, wherein the multimodal polyolefin is separatedinto fractions according to the following table: Sieve size FractionCollected Fraction Name 10 mesh >2000 μm Fraction 1 18 mesh 2000-1000 μmFraction 2 35 mesh <1000-500 μm Fraction 3 60 mesh <500-250 μm Fraction4 120 mesh <250-125 μm Fraction 5 200 mesh/Pan <125 μm Fraction 6

and the melt indices of Fractions 3,4 and 5 do not vary by marc than 30%relative to each other.
 18. The process of claim 3, wherein the Group 15containing catalyst compound is represented by the formulae;

wherein M is a Group 4,5, or 6 metal; each X is independently a leavinggroup; y is 0 or 1, wherein when y is 0, group L′ is absent; n is theoxidation state of M; m is the formal charge of the ligand representedby YZL and YZL′; L, L′, Y and Z are each a Group 15 element; R¹ and R²are independently a C₁ to C₂₀ hydrocarbon group, a heteroatom containinggroup having up to twenty carbon atoms, silicon, germanium, tin, lead,halogen or phosphorus; R³ is absent or a hydrocarbon group, hydrogen, ahalogen, a heteroatom containing group; R⁴ and R⁵ are independently analkyl group, an aryl group, substituted aryl group, a cyclic alkylgroup, a substituted cyclic alkyl group, a cyclic arylalkyl group, asubstituted cyclic arylalkyl group or multiple ring system; R⁶ and R⁷are independently absent, or hydrogen, an alkyl group, halogen,heteroatom or a hydrocarbyl group; and R⁺ is absent, or is hydrogen, aGroup 14 atom containing group, a halogen, or a heteroatom containinggroup.
 19. The process of claim 3, wherein the bulky ligand metallocenecatalyst compound is represented by the following formulae:L^(A)L^(B)MQ_(n) or L^(A)AL^(B)MQ_(n) wherein M is a Group 4, 5 or 6transition metal; bulky ligands L^(A) and L^(B) are each bound to M andare unsubstituted or substituted cyclopentadienyl ligands orcyclopentadienyl-type ligands, heteroatom substituted or heteroatomcontaining cyclopentadienyl-type ligands; Q is a monoanionic labileligand; wherein each Q is bound to M; A is a divalent bridging moietybound to each of L^(A) and L^(B); and n is 0, 1 or
 2. 20. The process ofclaim 1, wherein the support material is fumed silica.
 21. A film, pipeor blow molded product comprising the multimodal polyolefin of claim 1.